KR102353567B1 - Quick-hardening cement concrete composition having ultra high performance and repairing method for road and bridge concrete structure using the same - Google Patents

Abstract

The present invention relates to an ultra-high performance and ultra-rapid hardening cement concrete composition and a method for repairing a road and bridge concrete structure using the same. The composition comprises: 20-50 wt% of fine aggregate; 10-40 wt% of coarse aggregate; 10-40 wt% of an ultra-high performance binder; 0.5-20 wt% of an ultra-high performance modifier; and 0.1-5 wt% of water. The ultra-high performance binder comprises: 100 parts by weight of crude Portland cement; 20-40 parts by weight of calcium sulfoaluminate; 1-20 parts by weight of barium fluoride; 1-20 parts by weight of blast furnace slag fine powder; 1-20 parts by weight of ferronickel slag; 0.1-10 parts by weight of hollow activated carbon nanopowder; 0.1-10 parts by weight of spicule; and 0.1-10 parts by weight of lepidochrosite. The ultra-high performance modifier comprises: 100 parts by weight of acrylic latex; 20-50 parts by weight of an acrylonitrile-butadiene-styrene copolymer; 20-50 parts by weight of a polyvinyl acetate resin; 10-30 parts by weight of an aminomethyl polystyrene resin; 10-30 parts by weight of silk fibroin fiber; 0.1-10 parts by weight of epigallocatechin gallate; and 0.1-10 parts by weight of oryzanol. Accordingly, occurrence of cracks is inhibited by improving the structure and pore structure of a hardened product, water tightness and expression strength are enhanced, a traffic control time can be minimized by significantly increasing the curing speed of concrete, neutralization and corrosion of concrete caused by chloride are inhibited, and freeze-thaw resistance in response to a temperature change is improved such that the overall durability and life cycle of concrete can be extended.

Description

TECHNICAL FIELD [0002] Quick-hardening cement concrete composition having ultra high performance and repairing method for road and bridge concrete structure using the same}

The present invention suppresses cracking by improving the structure and pore structure of the hardening body, improves watertightness and expression strength, and greatly improves the curing speed of concrete to minimize traffic control time, and neutralization and corrosion of concrete by chloride The present invention relates to an ultra-high-performance super-fast-hardening cement concrete composition capable of extending the overall durability and life cycle of concrete by inhibiting and improving freeze-thaw resistance according to temperature changes, and a method for repairing concrete structures for roads and bridges using the same.

Concrete structures of roads and bridges may be damaged by deformation, cracking, and drop-off due to various factors such as overload, chloride penetration, and freeze-thaw. In addition, as the modernization and industrialization of our society is rapidly progressing, environmental pollution is becoming increasingly serious. Due to the increase in carbon dioxide and sulfur dioxide, which are harmful substances that corrode concrete, acidification of the atmosphere and acid rain accelerate the deterioration of concrete. , which exacerbates the above problem.

In particular, in the case of bridges, plastic deformation and damage due to impact caused by heavy vehicle traffic, climate change according to regional characteristics, effects on freeze and thaw, in the case of long bridges, effects due to deflection vibration, penetration of rainwater and chloride ions, etc. Damage is likely to occur due to the corrosion of the reinforcing bars and the promotion of damage to the concrete of the bridge deck. In addition, in the case of reinforced concrete, as the neutralization progresses, corrosion of the reinforcement is caused, and in severe cases, structural problems of the concrete structure also occur.

Therefore, since damage to concrete structures such as roads and bridges can lead to accidents while driving, urgent repair is required. In this way, when the road pavement is damaged, the damaged part must be removed and repaired. In particular, in the case of bridge repair, when the bridge is closed for a long period of time, traffic jams occur. needs to be done In addition, the bonding with the existing pavement should be excellent, and long-term strength and durability should be excellent, so that the maintenance effect should be maintained for a long time.

As a material for improving the above problems, a fast-hardening material is used to express fast structural strength, and the cement is mainly used for the initial-speed cement. It is used together with cement to repair roads and bridges.

However, there is a problem that the cement concrete composition containing such latex is greatly affected by the temperature according to the season, and the performance of the concrete may be greatly reduced according to the temperature difference. In particular, chloride penetration resistance, freeze-thaw stability, and scaling resistance are greatly reduced in winter, and after winter, surface peeling of latex-modified fast-hardening cement concrete, partial damage and dropping, portholes, and cracks due to drying shrinkage and relaxation stress occur. There are still problems such as

Republic of Korea Patent Registration No. 10-0943312 Republic of Korea Patent No. 10-1710300 Republic of Korea Patent No. 10-1831632

The present invention has been devised to solve the above problems, and one embodiment of the present invention improves the curing rate of concrete, suppresses cracks, improves watertightness and expression strength, and neutralizes and corrodes concrete by chloride It is an object of the present invention to provide an ultra-high performance super fast hardening cement concrete composition capable of suppressing and improving freeze-thaw resistance according to temperature changes, and a method of repairing concrete structures for roads and bridges using the same.

Various problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

An embodiment of the present invention comprises 20 to 50% by weight of fine aggregate, 10 to 40% by weight of coarse aggregate, 10 to 40% by weight of ultra-high performance binder, 0.5 to 20% by weight of ultra-high performance modifier and 0.1 to 5% by weight of water;

The ultra-high performance binder includes 100 parts by weight of crude steel portland cement, 20 to 40 parts by weight of calcium sulfoaluminate, 1 to 20 parts by weight of barium fluoride, 1 to 20 parts by weight of fine blast furnace slag powder, 1 to 20 parts by weight of ferronickel slag, hollow active 0.1 to 10 parts by weight of carbon nanopowder, 0.1 to 10 parts by weight of spicule, and 0.1 to 10 parts by weight of lepidocrosite;

The ultra-high performance modifier is 100 parts by weight of acrylic latex, 20 to 50 parts by weight of acrylonitrile-butadiene-styrene copolymer, 20 to 50 parts by weight of polyvinyl acetate resin, 10 to 30 parts by weight of aminomethyl polystyrene resin, 10 to 10 parts by weight of silk fibroin It provides an ultra-high performance super fast hardening cement concrete composition comprising 30 parts by weight, 0.1 to 10 parts by weight of epigallocatechin gallate, and 0.1 to 10 parts by weight of oryzanol.

The hollow activated carbon nanopowder is a hollow activated carbon nanopowder having crystals of metal sulfide on the surface;

The hollow activated carbon nanopowder having crystals of metal sulfide on the surface is a first electrospinning solution by dissolving a metal precursor, sulfur salt, polycarbonate (PC) and peroxyacetyl nitrate (PAN) in a first solvent. preparing; preparing a second electrospinning solution by dissolving polymethyl methacrylate (PMMA, Polymethyl methacrylate) in a second solvent; preparing a dual nozzle having the same axis as the outer nozzle and the inner nozzle, connecting the first electrospinning solution to the outer nozzle, and connecting the second electrospinning solution to the inner nozzle for electrospinning; A core in which a metal precursor, sulfur salt, and a first polymer are present in a shell portion formed by electrospinning through the outer nozzle, and a second polymer is present in a core portion formed by electrospinning through the inner nozzle - Forming a shell-shaped composite; pulverizing the core-shell-shaped composite to form a core-shell-shaped composite nanopowder; and heat treatment of the core-shell composite nanopowder in a reducing or inert atmosphere for thermal decomposition of the core part composed of the second polymer in the core-shell composite nanopowder, carbonization of the polymer of the shell part, and crystallization of metal sulfide It may be manufactured by a manufacturing method comprising the step of:

The metal precursor is iron (II) acetylacetonate (Fe(acac) ₂ ), iron (III) acetylacetonate (Fe (acetylacetonate) ₃ ), iron (II) acetate (Fe(ac) ₂ ), iron (III) ) acetate (Fe(ac) ₃ ), iron sulfamate (Fe(NH ₂ SO ₃ ) ₂ ), iron(II) stearate, iron(III) stearate, iron(II) laurate, iron(III) laurate, at least one iron precursor selected from the group consisting of iron (II) oleate, iron (III) oleate, and mixtures thereof; Copper acetate, copper acetylacetonate, copper i-butyrate, copper ethylacetoacetate, copper 2-ethylhexanoate, copper At least one copper precursor selected from the group consisting of gluconate, copper methoxide, copper neodecanoate, tetraaminecopper sulfate hydrate, and mixtures thereof A mixture of 1: 0.5 to 1 by weight was used;

The metal sulfide may include iron sulfide and copper sulfide.

The spicule is a needle-shaped Spongilla lacustris spicule whose surface is modified to be hydrophilic;

For the needle-shaped Spongilla lacustris spicules whose surface was modified to be hydrophilic, the crushed Spongilla lacustris spicules were loaded with hydrochloric acid solution, and then heated and sonicated by adding hydrogen peroxide to extract Spongilla lacustris spicules. to do; After supporting the extracted Spongilla lacustris spicules in hydrochloric acid solution, washing with phosphate buffered saline to neutralize the acidity and drying to obtain needle-shaped Spongilla lacustris spicules; reacting the needle-shaped Spongilla lacustris spicule and hydrogen peroxide for 6 to 20 hours to form pores on the surface of the needle-shaped Spongilla lacustris spicule; and reacting a needle-shaped Spongilla lacustris spicule having pores on the surface with a basic compound to modify the surface to be hydrophilic.

Another embodiment of the present invention is a method of repairing concrete structures for roads and bridges using the ultra-high performance super fast hardening cement concrete composition,

removing the deteriorated, damaged or contaminated parts of road and bridge concrete structures; cleaning the removed area; Primer or blooming treatment on the cleaned area; pouring the ultra-high-performance super-fast hardening cement concrete composition on the primer or blooming-treated top; After pouring, the step of tinting to increase the crack induction and slip resistance; Spraying a curing agent to prevent initial plastic cracking by preventing evaporation of moisture in the upper part after the tinting step; And it provides a method for repairing concrete structures of roads and bridges comprising the step of curing.

According to the ultra-high performance super fast hardening cement concrete composition according to an embodiment of the present invention and the repair method for road and bridge concrete structures using the same, by improving the structure and pore structure of the hardened body and suppressing cracks, and enhancing watertightness and expression strength , has the effect of improving the mechanical properties of concrete structures. In addition, the overall durability and life cycle of concrete can be minimized by significantly improving the curing speed of concrete, suppressing neutralization and corrosion of concrete by chloride, and improving freeze-thaw resistance according to temperature changes. has the effect of prolonging

Hereinafter, embodiments of the present invention will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

An embodiment of the present invention comprises 20 to 50% by weight of fine aggregate, 10 to 40% by weight of coarse aggregate, 10 to 40% by weight of ultra-high performance binder, 0.5 to 20% by weight of ultra-high performance modifier and 0.1 to 5% by weight of water;

The ultra-high performance binder includes 100 parts by weight of crude steel portland cement, 20 to 40 parts by weight of calcium sulfoaluminate, 1 to 20 parts by weight of barium fluoride, 1 to 20 parts by weight of fine blast furnace slag powder, 1 to 20 parts by weight of ferronickel slag, hollow active 0.1 to 10 parts by weight of carbon nanopowder, 0.1 to 10 parts by weight of spicule, and 0.1 to 10 parts by weight of lepidocrosite;

The ultra-high performance modifier is 100 parts by weight of acrylic latex, 20 to 50 parts by weight of acrylonitrile-butadiene-styrene copolymer, 20 to 50 parts by weight of polyvinyl acetate resin, 10 to 30 parts by weight of aminomethyl polystyrene resin, 10 to 10 parts by weight of silk fibroin It provides an ultra-high performance super fast hardening cement concrete composition comprising 30 parts by weight, 0.1 to 10 parts by weight of epigallocatechin gallate, and 0.1 to 10 parts by weight of oryzanol.

According to the ultra-high performance super fast hardening cement concrete composition according to an embodiment of the present invention and the repair method for road and bridge concrete structures using the same, the structure and pore structure of the hardened body are improved to suppress cracks, and water tightness and expression strength are improved This has the effect of improving the mechanical properties of the concrete structure. In addition, the overall durability and life cycle of concrete can be minimized by significantly improving the curing speed of concrete, suppressing neutralization and corrosion of concrete by chloride, and improving freeze-thaw resistance according to temperature changes. has the effect of prolonging

The ultra-high performance super fast hardening cement concrete composition according to an embodiment of the present invention contains 20 to 50% by weight of fine aggregate, 10 to 40% by weight of coarse aggregate, 10 to 40% by weight of ultrahigh performance binder, 0.5 to 20% by weight of ultrahigh performance modifier and water 0.1 to 5% by weight.

The aggregate used in the present invention is divided into fine aggregate and coarse aggregate. Those having a particle diameter of 5 mm or less are called fine aggregates, and those having a particle diameter greater than 5 mm are called coarse aggregates. The fine aggregate is preferably contained in an amount of 20 to 50% by weight based on the ultra-high performance super fast hardening cement concrete composition of the present invention, and the coarse aggregate is preferably contained in an amount of 10 to 40% by weight based on the ultra high performance super fast hardening cement concrete composition of the present invention. .

First, the ultra-high performance binder is 100 parts by weight of crude steel Portland cement, 20 to 40 parts by weight of calcium sulfoaluminate, 1 to 20 parts by weight of barium fluoride, 1 to 20 parts by weight of fine blast furnace slag powder, 1 to 20 parts by weight of ferronickel slag, A hollow activated carbon nanopowder containing 0.1 to 10 parts by weight, 0.1 to 10 parts by weight of spicule, and 0.1 to 10 parts by weight of lepidochrosite may be used.

It is preferable to use the crude Portland cement specified in KS, and it is preferable to use a powder having a fineness of 4,500 to 9,000 cm2/g.

Hereinafter, the content of other components constituting the ultra-high performance binder is based on 100 parts by weight of the crude Portland cement.

The calcium sulfoaluminate functions to provide fast curing properties.

The calcium sulfoaluminate is preferably contained in an amount of 20 to 40 parts by weight based on 100 parts by weight of the crude Portland cement. If the content of the calcium sulfoaluminate is too small, there is a problem that the above-described improvement effect may be insufficient. There is a problem in that price competitiveness may be lowered.

The barium fluoride functions to improve strength expression such as bending and adhesive strength, water tightness, corrosion resistance, salt damage and freeze-thaw resistance, and to provide a shrinkage prevention effect.

The barium fluoride is preferably contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the crude steel portland cement. When the content of the barium fluoride is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the barium fluoride is too large, the curing rate is lowered or the manufacturing cost is increased, so that the price competitiveness can be lowered. have.

The fine powder of blast furnace slag functions to express long-term strength and improve durability with latent hydraulic properties.

The fine powder of blast furnace slag is preferably contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the crude steel portland cement. When the content of the fine blast furnace slag powder is too small, the above-described improvement effect may be insufficient, and when the content of the fine blast furnace slag fine powder is too large, there is a problem that the curing speed may decrease.

The ferronickel slag refers to slag generated during a smelting reduction process in an electric furnace during the production of ferronickel in a ferronickel factory, and functions to improve strength expression and watertightness, and to provide an effect of preventing shrinkage.

More specifically, the ferronickel slag has a SiO ₂ content of 50 to 70 wt%, a MgO content of 25 to 45 wt%, a CaO content of 0.1 to 3 wt%, and a Fe ₂ O ₃ content of 1 to 10% by weight, _{the content of Al 2} O ₃ is 0.1 to 3% by weight, the content of NiO is 0.1 to 3% by weight, and _{the content of Cr 2} O ₃ is 0.1 to 3% by weight. In addition to being able to further improve the crack control effect, there is an effect that can further improve the excellent crack control effect.

The ferronickel slag is preferably contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the crude steel portland cement. If the content of the ferronickel slag is too small, there is a problem that the above improvement effect may be insufficient. There is a problem that can be degraded.

The hollow activated carbon nanopowder functions to improve resistance to salt damage and freeze-thaw, and to provide heat resistance, abrasion resistance and anti-shrinkage effect along with an excellent strength expression effect.

More specifically, the hollow activated carbon nanopowder is a hollow activated carbon nanopowder having crystals of metal sulfide on the surface, so that the above-described effect can be further improved, and the effect of improving fast curing properties is have.

The hollow activated carbon nanopowder having crystals of metal sulfide on the surface is a first electrospinning solution by dissolving a metal precursor, sulfur salt, polycarbonate (PC) and peroxyacetyl nitrate (PAN) in a first solvent. to prepare; preparing a second electrospinning solution by dissolving polymethyl methacrylate (PMMA, Polymethyl methacrylate) in a second solvent; preparing a dual nozzle having the same axis as the outer nozzle and the inner nozzle, connecting the first electrospinning solution to the outer nozzle, and connecting the second electrospinning solution to the inner nozzle for electrospinning; A core in which a metal precursor, sulfur salt, and a first polymer are present in a shell portion formed by electrospinning through the outer nozzle, and a second polymer is present in a core portion formed by electrospinning through the inner nozzle - Forming a shell-shaped composite; pulverizing the core-shell-shaped composite to form a core-shell-shaped composite nanopowder; and heat treatment of the core-shell composite nanopowder in a reducing or inert atmosphere for thermal decomposition of the core part composed of the second polymer in the core-shell composite nanopowder, carbonization of the polymer of the shell part, and crystallization of metal sulfide It may be manufactured by a manufacturing method comprising the step of:

In this case, the first electrospinning solution is 5 to 15 parts by weight of a metal precursor, 0.5 to 5 parts by weight of sulfur salt, 1 to 10 parts by weight of polycarbonate (PC), and 5 to 15 parts by weight of peroxyacetyl nitrate (PAN) Part prepared by dissolving 100 parts by weight of the first solvent may be preferably used; The second electrospinning solution may preferably be prepared by dissolving 5 to 30 parts by weight of polymethyl methacrylate (PMMA) in 100 parts by weight of the second solvent to prepare the second electrospinning solution.

In addition, as the metal precursor, one or more metal precursors selected from the group consisting of iron, copper, molybdenum, tungsten, tin, and mixtures thereof may be used.

More specifically, the iron precursor is iron (II) acetylacetonate (Fe(acac) ₂ ), iron (III) acetylacetonate (Fe (acetylacetonate) ₃ ), iron (II) acetate (Fe(ac) ₂ ) , iron(III) acetate (Fe(ac) ₃ ), iron sulfamate (Fe(NH ₂ SO ₃ ) ₂ ), iron(II) stearate, iron(III) stearate, iron(II) laurate, iron laurate (III), iron (II) oleate, iron (III) oleate, and at least one member selected from the group consisting of mixtures thereof can be preferably used; The copper precursor is copper acetate, copper acetylacetonate, copper isobutyrate (Copper i-butyrate), copper ethyl acetoacetate (Copper ethylacetoacetate), copper 2-ethylhexanoate (Copper 2- 1 selected from the group consisting of ethylhexanoate), copper gluconate, copper methoxide, copper neodecanoate, tetraamminecopper sulfate hydrate, and mixtures thereof More than one species can be preferably used; The molybdenum precursor is ammonium tetrathiomolybdate, ammonium heptamolybdate, ammonium tetrathiomolybdate, sodium molybdate (Sodium molybdate), trithiochloro molybdate (Trithio-chloro molybdate) and at least one selected from the group consisting of mixtures thereof may be preferably used; The tungsten precursor is ammonium tungstate, sodium tungstate, ammonium tetrathiotungstate, tungsten hexacarbonyl, tungsten chloride, tungsten fluoride ( Tungsten fluoride) and at least one selected from the group consisting of mixtures thereof may be preferably used, and the tin precursor is tin chloride, sodium diethyldithiocarbamate trihydrate, At least one selected from the group consisting of tin nitride and mixtures thereof may be preferably used.

More preferably, the metal precursor is iron(II) acetylacetonate (Fe(acac) ₂ ), iron(III) acetylacetonate (Fe(acetylacetonate) ₃ ), iron(II) acetate (Fe(ac) ₂ ), iron (III) acetate (Fe(ac) ₃ ), iron sulfamate (Fe(NH ₂ SO ₃ ) ₂ ), iron (II) stearate, iron (III) stearate, iron laurate (II), iron laurate (III) ), iron (II) oleate, iron (III) oleate, and at least one iron precursor selected from the group consisting of mixtures thereof; Copper acetate, copper acetylacetonate, copper i-butyrate, copper ethylacetoacetate, copper 2-ethylhexanoate, copper At least one copper precursor selected from the group consisting of gluconate, copper methoxide, copper neodecanoate, tetraaminecopper sulfate hydrate, and mixtures thereof By using a mixture of 1: 0.5 to 1 weight ratio, there is an effect that the above-described effect can be further improved by using a hollow activated carbon nanopowder having crystals of iron sulfide and copper sulfide on the surface.

In addition, the sulfur salt may preferably be at least one selected from the group consisting of thiourea, sulfur, and mixtures thereof.

In addition, the first solvent and the second solvent may be the same or different from each other, and each independently distilled water (Distilled Water), dimethylformamide (DMF, Dimethylformamide), dimethylacetamide (DMAc, Dimethylacetamide), ethanol (Ethanol) ), acetone (Acetone), tetrahydrofuran (Tetrahydrofuran), dimethyl sulfoxide (DMSO, dimethyl sulfoxide), ethylene glycol (EG, Ethylene glycol), and at least one selected from the group consisting of mixtures thereof can be preferably used. have.

In addition, the electrospinning can form a stable hollow structure when the speed of the spinning solution discharged to the outer nozzle is slower than the speed of the spinning solution discharged by the inner nozzle. At this time, the discharge rate of the outer nozzle may be appropriately selected depending on the viscosity of the spinning solution in the range of 0.2 to 500 μL/min, and in the case of the discharge rate of the inner nozzle, it may be discharged in the range of 0.1 to 250 μL/min. . In addition, the voltage applied to the dual nozzle may be performed in the range of 5 to 30 kV.

In addition, the step of pulverizing the core-shell-shaped composite to form a core-shell-shaped composite nanopowder; -Methylpyrrolidone, acetonitrile, methylene chloride, and after impregnation in one or more solvents selected from the group consisting of mixtures thereof, microbead grinding using zirconia balls having an average diameter of 0.015 to 0.1 mm Can be carried out have.

In addition, the heat treatment _{may be performed in a mixed gas atmosphere in which nitrogen (N 2} ) and hydrogen sulfide (H ₂ S) are mixed in a volume ratio of 1: 0.1 to 0.3, in a temperature range of 500 to 800 °C.

The hollow activated carbon nanopowder may have a diameter of 0.3 to 1.5 μm of a hollow core and a thickness of 100 nm to 300 nm of the shell.

The hollow activated carbon nanopowder is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the crude Portland cement. When the content of the hollow activated carbon nanopowder is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the hollow activated carbon nanopowder is too large, the manufacturing cost increases and the price competitiveness may be lowered. There is this.

The spicule functions to improve resistance to salt damage and freeze-thaw, and to provide heat resistance, abrasion resistance, microcrack prevention and shrinkage prevention effects along with an excellent strength expression effect.

More specifically, the spicule has the effect of further improving the above-described effect by using a needle-shaped Spongilla lacustris spicule whose surface is modified to be hydrophilic.

The needle-shaped Spongilla lacustris spicules modified with hydrophilicity of the above-mentioned surface were prepared by supporting crushed Spongilla lacustris spicules with hydrochloric acid solution, then heating and sonicating with hydrogen peroxide. extracting; After supporting the extracted Spongilla lacustris spicules in hydrochloric acid solution, washing with phosphate buffered saline to neutralize the acidity and drying to obtain needle-shaped Spongilla lacustris spicules; reacting the needle-shaped Spongilla lacustris spicule and hydrogen peroxide for 6 to 20 hours to form pores on the surface of the needle-shaped Spongilla lacustris spicule; and reacting a basic compound with a needle-shaped Spongilla lacustris spicule having pores on the surface to modify the surface to be hydrophilic.

In this case, the basic compound is generally known in the art, and the type thereof is not particularly limited, but calcium hydroxide (Ca(OH) ₂ ) at a concentration of 3 to 7 N and magnesium hydroxide (Mg(OH) at a concentration of 3 to 7 N) ) ₂ ) is mixed in a volume ratio of 1: 0.1 to 0.5 to obtain an excellent effect of improving long-term strength.

The spicule is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the crude Portland cement. When the content of the spicule is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the spicule is too large, there is a problem that the manufacturing cost increases and price competitiveness may decrease.

The lepidochrosite is an iron oxide-based compound, and it functions to exhibit excellent strength, prevent shrinkage, and improve abrasion resistance, and assist in fast curing properties, thereby exhibiting super-fast hardness.

More specifically, the lepidochrosite may be used to have a specific surface area of ^{50 to 200 g/m 2 to further enhance the above-described effect.}

The lepidochrosite is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the crude Portland cement. When the content of the lepidochrosite is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the lepidocrosite is too large, there is a problem that the manufacturing cost increases and the price competitiveness may decrease. .

In addition, the ultra-high performance binder is an additive generally used in the art, and may further include at least one selected from the group consisting of a curing accelerator, a setting retarder, a water reducing agent, a material separation preventing agent, and mixtures thereof.

More specifically, the curing accelerator functions to further activate the hydration reaction of the composition to express compressive strength at an early stage. In consideration of this function, the curing accelerator is preferably contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the crude Portland cement.

In addition, the curing accelerator is generally used in the art, for example, calcium formate, calcium chloride, calcium salt such as calcium nitrate, chloride such as magnesium chloride, magnesium sulfate, sulfate such as aluminum sulfate, potassium hydroxide, sodium hydroxide , carbonates such as sodium carbonate, formic acid or a salt thereof, lithium carbonate, and the like can be used.

The setting delay agent functions to maintain the initial working time and improve workability. In consideration of these functions, the setting retardant is preferably contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the crude Portland cement.

In addition, the setting delay agent is generally used in the art, for example, glucose, glucose, dextrin, sugars such as dextran, gluconic acid, tartaric acid, malic acid, citric acid, citric acid, such as boric acid Acids or salts thereof, aminocarboxylic acids or salts thereof, phosphonic acid or derivatives thereof, polyvinyl alcohol, polyalcohols such as glycerin, and the like can be used.

The water reducing agent functions to temporarily improve fluidity by dispersing the particles by repulsive force between the particles. The water reducing agent is preferably contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the crude Portland cement.

In addition, the water-reducing agent is generally used in the art, for example, a naphthalene-based, melamine-based, polycarboxylic acid-based water-reducing agent may be used. More preferably, it is good to use a polycarboxylic acid-based water reducing agent.

The material separation preventing agent functions to prevent material separation of the composition and improve workability. The material separation preventing agent is preferably contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the crude Portland cement.

In addition, the material separation preventing agent is generally used in the art, for example, methyl cellulose, starch, gum (Gum), etc. may be used. More preferably, it is good to use a starch-based material separation preventing agent with a small decrease in strength.

On the other hand, the ultra-high performance modifier functions to improve the curing time, workability, strength and durability of the ultra-high performance ultra-fast hardening cement concrete composition of the present invention.

The ultra-high performance modifier is preferably contained in an amount of 0.5 to 20 wt % in the ultra high performance ultra fast hardening cement concrete composition of the present invention. When the content of the ultra-high-performance modifier is too small, the above-described improvement effect may be weak, and when the content of the ultra-high-performance modifier is too large, the viscosity is lowered and the workability (slump) can be improved, but by delaying the hydration reaction There is a problem in that the rapid hardening property is lowered or the manufacturing cost is increased, so that the price competitiveness may be lowered.

The ultra-high performance modifier is 100 parts by weight of acrylic latex, 20 to 50 parts by weight of acrylonitrile-butadiene-styrene copolymer, 20 to 50 parts by weight of polyvinyl acetate resin, 10 to 30 parts by weight of aminomethyl polystyrene resin, 10 to 10 parts by weight of silk fibroin 30 parts by weight, 0.1 to 10 parts by weight of epigallocatechin gallate, and 0.1 to 10 parts by weight of oryzanol may be used.

The acrylic latex functions to greatly enhance the bending, tensile and adhesion strength.

The acrylic latex is 30 to 50% by weight of methyl methacrylate (MMA), 5 to 20% by weight of acrylic acid normal butyl ester (BA: Butyl Acrylate Monomer), 0.1 to 10% by weight of acrylonitrile, dimethylammono The above effects can be achieved by using a monomer composition for polymerization containing 0.1 to 10 wt% of ethylmethyl acrylate and 30 to 50 wt% of 2-ethylhexyl acrylate (2-EHA: 2-Ethyl Hexylacrylate). can be further improved.

Hereinafter, the content of other components constituting the ultra-high performance modifier is based on 100 parts by weight of the acrylic latex.

The acrylonitrile-butadiene-styrene copolymer functions to improve water resistance, alkali resistance, and weather resistance as well as improve warpage, tensile and adhesion strength with excellent adhesion.

The acrylonitrile-butadiene-styrene copolymer is preferably contained in an amount of 20 to 50 parts by weight based on 100 parts by weight of the acrylic latex. When the content of the acrylonitrile-butadiene-styrene copolymer is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the acrylonitrile-butadiene-styrene copolymer is too large, the durability performance decreases There are problems that could be.

The polyvinyl acetate resin functions to enhance bending, tensile and adhesive strength. In addition, it prevents material separation, improves tensile strength, suppresses cracking, reduces crack width after cracking, and improves durability.

The polyvinyl acetate resin is preferably contained in an amount of 20 to 50 parts by weight based on 100 parts by weight of the acrylic latex. When the content of the polyvinyl acetate resin is too small, there is a problem that the improvement effect may be insufficient, and when the content of the polyvinyl acetate resin is too large, there is a problem that durability performance may be reduced.

The aminomethyl polystyrene resin functions to enhance warpage, tensile strength and adhesion strength. In addition, it prevents material separation, improves tensile strength, suppresses cracking, reduces crack width after cracking, and improves durability.

The aminomethyl polystyrene resin is preferably contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the acrylic latex. When the content of the aminomethyl polystyrene resin is too small, the improvement effect may be insufficient, and when the content of the aminomethyl polystyrene resin is too large, there is a problem that price competitiveness may be lowered.

The silk fibroin functions to enhance flexural, tensile and adhesive strength. In addition, it prevents material separation, improves tensile strength, suppresses cracking, reduces the width of cracks after cracks occur, and improves durability such as watertightness, waterproofness and rust prevention.

The silk fibroin is preferably purified by putting silk complex into a sodium carbonate (Na ₂ CO ₃ ) solution when the solution becomes transparent, boiling, and then dissolving the dried silk in a lithium bromide (LiBr) solution, dialyzing for 2 to 5 days, and filtering. can be used

The silk fibroin is preferably contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the acrylic latex. When the content of silk fibroin is too small, there is a problem that the improvement effect may be insufficient, and when the content of silk fibroin is too large, there is a problem that the initial strength may be lowered or price competitiveness may be lowered.

The epigallocatechin gallate serves to provide excellent workability and excellent miscibility between materials, and to improve durability such as resistance to salt damage, neutralization, and freeze damage, water permeability resistance, chemical resistance, waterproofness and rust prevention.

The epigallocatechin gallate is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic latex. When the content of epigallocatechin gallate is too small, the above-described improvement effect may be insufficient. There are problems that could be.

The oryzanol functions to provide excellent workability by enhancing the initial adhesion strength, preventing material separation, and suppressing crack generation.

The oryzanol is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic latex. When the content of oryzanol is too small, the improvement effect may be insufficient, and when the content of oryzanol is too large, there is a problem in that durability or price competitiveness may decrease.

In addition, the ultra-high-performance modifier provides excellent bonding strength, thereby further enhancing bending, tensile and adhesion strength, as well as improving particularly excellent crack resistance and shrinkage resistance, resistance to salt damage, neutralization, frost damage, etc., water permeability resistance, waterproofness, etc. In order to improve the durability of the ceramide-based derivative represented by the following formula (1) may be further included.

[Formula 1]

In the above formula,

R ₁ and R ₂ are each independently at least one selected from the group consisting of linear or branched (C7 to C30)alkyl, (C7 to C30)alkenyl, and mixed functional groups thereof.

More specifically, the ceramide-based derivative is obtained by using a mixture of a ceramide-based derivative represented by the following Chemical Formula 1-1 and a ceramide-based derivative represented by the following Chemical Formula 1-2 in a ratio of 1: 2 to 5, by weight. Not only can it be further improved, but there is an effect that can provide durability such as particularly excellent water permeability resistance and waterproofness.

[Formula 1-1]

[Formula 1-2]

The ceramide-based derivative represented by Formula 1 is preferably contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the acrylic latex. When the content of the ceramide-based derivative represented by Formula 1 is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the ceramide-based derivative represented by Formula 1 is too large, the performance improvement effect is further There is a problem in that price competitiveness may be lowered due to the high production cost and the production cost.

In addition, the ultra-high performance modifier is an additive generally used in the art, and may further include one or more selected from the group consisting of an antifoaming agent, an air entraining agent, and mixtures thereof.

More specifically, the anti-foaming agent functions to further improve strength and durability by reducing the amount of air and removing entrapped air and voids in the concrete. In consideration of this function, the antifoaming agent is preferably contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the acrylic latex.

In addition, the anti-foaming agent is generally used in the art, for example, a silicone-based anti-foaming agent, a fatty acid-based anti-foaming agent, an oil-based anti-foaming agent, an ester-based anti-foaming agent, an oxyalkylene-based anti-foaming agent, an alcohol-based anti-foaming agent and the like may be used. The silicone-based antifoaming agent includes dimethyl silicone oil, polyorganosiloxane, fluorosilicone oil, and the like, and the fatty acid-based antifoaming agent includes stearic acid and oleic acid. In addition, the oil-based anti-foaming agent includes kerosene, animal and vegetable oil, castor oil, and the like, and the ester-based anti-foaming agent includes solitol trioleate, glycerol monoricinolate, and the like. In addition, the oxyalkylene-based antifoaming agent includes polyoxyalkylene, acetylene ethers, polyoxyalkylene fatty acid ester, polyoxyalkylenealkylamine, and the like, and the alcohol-based antifoaming agent includes glycol.

The air entraining agent functions to improve workability by improving the dispersibility of the composition. In consideration of these functions, the air entraining agent is preferably contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the acrylic latex.

In addition, the air entraining agent is generally used in the art, for example, there are polycarboxylic acid-based, naphthalene-based, melamine-based, and the like. More preferably, the air entraining agent is a polycarboxylic acid-based air entraining agent.

The ultra-high performance super fast hardening cement concrete composition according to a preferred embodiment of the present invention is prepared by stirring 20 to 50 wt % of fine aggregate, 10 to 40 wt % of coarse aggregate, and 10 to 40 wt % of ultra high performance binder in a forced mixer, followed by an ultra high performance modifier 0.5 to 20% by weight and 0.1 to 5% by weight of water may be further mixed and stirred for a predetermined time (eg, 1 to 10 minutes).

In addition, another embodiment of the present invention is a method of repairing concrete structures for roads and bridges using the ultra-high performance super fast hardening cement concrete composition,

removing the deteriorated, damaged or contaminated parts of road and bridge concrete structures; cleaning the removed area; Primer or blooming treatment on the cleaned area; pouring the ultra-high-performance super-fast hardening cement concrete composition on the primer or blooming-treated top; After pouring, the step of tinting to increase the crack induction and slip resistance; Spraying a curing agent to prevent initial plastic cracking by preventing evaporation of moisture in the upper part after the tinting step; And it provides a method for repairing concrete structures of roads and bridges comprising the step of curing.

More specifically, the step of removing the deteriorated, damaged or contaminated portion of the road and bridge concrete structures; the deteriorated, damaged or contaminated portions of the road and bridge concrete structures using a crusher, planer, shot blaster or waterjet It can be done by cutting and blasting.

In addition, the step of treating the cleaned area with a primer or blooming; may be used to refer to an operation of facilitating attachment of the ultra-high-performance super-fast hardening cement concrete composition according to an embodiment of the present invention to a concrete slab.

In this case, as the primer material, at least one selected from polyacrylic ester (PAE), epoxy emulsion, ethyl vinyl acetate (EVA), and acrylic emulsion may be selected and used.

In addition, as the blooming material, at least one selected from poly acrylic ester (PAE), epoxy emulsion, ethyl vinyl acetate (EVA) and acrylic emulsion may be selected and used.

In addition, in the curing step, depending on the atmospheric conditions including the temperature, humidity, and wind strength of the site, 1) spraying only the curing agent, or 2) after spraying the curing agent, cover the top with a vinyl or curing cloth and water it. It is recommended to separate the curing steps while maintaining the wet state, or 3) using a vinyl, curing cloth, or a thermal insulation cover after the curing agent is sprayed.

In particular, in the curing step, in the case of on-site atmospheric conditions (for example, in the case of atmospheric conditions with high atmospheric temperature (25 ℃ or more), low relative humidity, and windy conditions, such as in summer, vinyl, curing cloth, etc. Conversely, if the atmospheric temperature (below 25℃) is not high, relative humidity is high, and there is little wind, spray only curing agent and cure according to). After spraying, cover the top with vinyl, curing cloth, etc. In addition, when the atmospheric temperature is 5 ℃ or less, after spraying the curing agent, it may further include the step of performing thermal insulation curing using vinyl, curing cloth, insulation cover, etc.

According to the ultra-high performance super fast hardening cement concrete composition according to an embodiment of the present invention and the repair method for road and bridge concrete structures using the same, by improving the structure and pore structure of the hardened body and suppressing cracks, and enhancing watertightness and expression strength , has the effect of improving the mechanical properties of concrete structures. In addition, it is possible to minimize the traffic control time by significantly improving the curing speed of concrete, suppress the neutralization and corrosion of concrete by chloride, and improve the freeze-thaw resistance according to temperature changes, thereby improving the overall durability and life cycle of concrete. has the effect of prolonging the

As mentioned above, although preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the scope of the technical spirit of the present invention. This is possible.

<Production Example 1>

Preparation of hollow activated carbon nanopowder

A first electrospinning solution was prepared by dissolving 9 parts by weight of polycarbonate (PC) and 14 parts by weight of peroxyacetyl nitrate (PAN) in 100 parts by weight of tetrahydrofuran. Separately, a second electrospinning solution was prepared by dissolving 28 parts by weight of polymethyl methacrylate (PMMA) in 100 parts by weight of tetrahydrofuran.

Meanwhile, by preparing a dual nozzle having the same axis as the outer nozzle and the inner nozzle, the first electrospinning solution was connected to the outer nozzle, and the second electrospinning solution was connected to the inner nozzle to perform electrospinning. At this time, the discharge rate of the outer nozzle was 1.2 μL/min, the discharge rate of the inner nozzle was 0.5 μL/min, and the voltage applied to the dual nozzle was 10 kV.

Thus, a core-shell-shaped composite was formed, and the core-shell-shaped composite was impregnated in N-methylpyrrolidone solvent, and then microbeads were pulverized using zirconia balls having an average diameter of 0.055 mm. A shell-shaped composite nanopowder was formed.

By heat-treating the core-shell-shaped composite nanopowder in a nitrogen (N ₂ ) atmosphere at a temperature range of 550 ° C., a hollow activated carbon nanopowder having a diameter of 0.47 μm and a shell thickness of 183 nm prepared.

<Preparation Example 2>

Preparation of hollow activated carbon nanopowder with iron sulfide crystals on the surface

Iron (III) acetylacetonate (Fe (acetylacetonate) ₃ ) 7 parts by weight, thiourea (Thiourea) 0.7 parts by weight, polycarbonate (PC) 7 parts by weight, and peroxyacetyl nitrate (PAN) 13.3 parts by weight A first electrospinning solution was prepared by dissolving parts in 100 parts by weight of tetrahydrofuran. Separately, a second electrospinning solution was prepared by dissolving 28 parts by weight of polymethyl methacrylate (PMMA) in 100 parts by weight of tetrahydrofuran.

On the other hand, by preparing a dual nozzle having the same axis as the outer nozzle and the inner nozzle, the first electrospinning solution was connected to the outer nozzle, and the second electrospinning solution was connected to the inner nozzle to perform electrospinning. At this time, the discharge rate of the outer nozzle was 1.2 μL/min, the discharge rate of the inner nozzle was 0.5 μL/min, and the voltage applied to the dual nozzle was 10 kV.

Thus, a core-shell-shaped composite was formed, and the core-shell-shaped composite was impregnated in N-methylpyrrolidone solvent, and then microbeads were pulverized using zirconia balls having an average diameter of 0.055 mm. A shell-shaped composite nanopowder was formed.

The core-shell-shaped composite nanopowder _{is heat-treated at a temperature of 600 ° C. in a mixed gas atmosphere in which nitrogen (N 2} ) and hydrogen sulfide (H ₂ S) are mixed at a volume ratio of 1: 0.2, the diameter of the hollow core part A hollow activated carbon nanopowder having iron sulfide crystals on the surface of which silver was 0.38 μm and the shell had a thickness of 205 nm was prepared.

<Production Example 3>

Preparation of hollow activated carbon nanopowder having iron sulfide and copper sulfide crystals on the surface

Iron (III) acetylacetonate (Fe (acetylacetonate) ₃ ) and copper gluconate (Copper gluconate) 1: 0.7 weight ratio of a mixture of metal precursor 5 parts by weight, thiourea (Thiourea) 1.3 parts by weight, polycarbonate ( A first electrospinning solution was prepared by dissolving 7 parts by weight of PC) and 13.7 parts by weight of peroxyacetyl nitrate (PAN) in 100 parts by weight of tetrahydrofuran. Separately, a second electrospinning solution was prepared by dissolving 28 parts by weight of polymethyl methacrylate (PMMA) in 100 parts by weight of tetrahydrofuran.

On the other hand, by preparing a dual nozzle having the same axis as the outer nozzle and the inner nozzle, the first electrospinning solution was connected to the outer nozzle, and the second electrospinning solution was connected to the inner nozzle to perform electrospinning. At this time, the discharge rate of the outer nozzle was 1.2 μL/min, the discharge rate of the inner nozzle was 0.5 μL/min, and the voltage applied to the dual nozzle was 10 kV.

Thus, a core-shell-shaped composite was formed, and the core-shell-shaped composite was impregnated in N-methylpyrrolidone solvent, and then microbeads were pulverized using zirconia balls having an average diameter of 0.055 mm. A shell-shaped composite nanopowder was formed.

The core-shell-shaped composite nanopowder _{is heat-treated at a temperature of 600 ° C. in a mixed gas atmosphere in which nitrogen (N 2} ) and hydrogen sulfide (H ₂ S) are mixed at a volume ratio of 1: 0.2, the diameter of the hollow core part A hollow activated carbon nanopowder having iron sulfide and copper sulfide crystals on the surface of which silver was 0.41 μm and the shell had a thickness of 212 nm was prepared.

<Production Example 4>

Preparation of needle-shaped Spongilla lacustris spicules with pores formed on the surface

After supporting the crushed Spongilla lacustris in 0.1M hydrochloric acid solution for 15 minutes, adding 5 ml/g of 30% (w/w) hydrogen peroxide and heating for 2 hours, 300 W and 40 kHz conditions for 1 hour After sonicating for a while, filtration and washing with 500 ml of purified water were repeated three times to extract Spongilla lacustris spicules.

After that, the extracted Spongilla lacustris spicules were supported in 0.5 M hydrochloric acid solution for 1 day, washed with phosphate buffered saline to neutralize acidity, washed 3 times with purified water, and dried at 50 ° C. I got my brother's Spongilla Lacustris Spicule.

Then, 20 ml/g of 35% (w/w) hydrogen peroxide was added to the needle-shaped Spongilla lacustris spicule, stirred and reacted for 15 hours, and pores ( pores) were formed. Thereafter, the process of filtration and washing with 500 ml of purified water was repeated 3 times, and then dried at 50° C. to obtain a needle-shaped Spongilla lacustris spicule with pores formed on the surface.

<Preparation Example 5>

Preparation of needle-shaped Spongilla lacustris spicules modified with hydrophilic surface

The crushed Spongilla lacustris was supported for 15 minutes with 0.1M hydrochloric acid solution, then 5 ml/g of 30% (w/w) hydrogen peroxide was added and heated for 2 hours, and then heated for 2 hours at 300 W and 40 kHz conditions for 1 hour. After sonicating for a while, filtration and washing with 500 ml of purified water were repeated three times to extract Spongilla lacustris spicules.

After that, the extracted Spongilla lacustris spicule was supported in 0.5 M hydrochloric acid solution for 1 day, washed with phosphate buffered saline to neutralize acidity, washed 3 times with purified water, and dried at 50 ° C. I got my brother's Spongilla Lacustris Spicule.

Then, 20 ml/g of 35% (w/w) hydrogen peroxide was added to the needle-shaped Spongilla lacustris spicule, stirred and reacted for 15 hours, and pores ( pores) were formed. Thereafter, the process of filtration and washing with 500 ml of purified water was repeated three times, and then dried at 50° C. to obtain a needle-shaped Spongilla lacustris spicule with pores formed on the surface.

10 ml/g of 1N NaOH was added to the needle-shaped Spongilla lacustris spicules having pores formed on the surface and reacted at 40° C. for 1 hour. Thereafter, the process of filtration and washing with 500 ml of purified water was repeated three times, and then dried at 50° C. to obtain a needle-shaped Spongilla lacustris spicule whose surface was modified to be hydrophilic (hydroxyl group).

<Preparation Example 6>

Preparation of needle-shaped Spongilla lacustris spicules modified with hydrophilic surface

The crushed Spongilla lacustris was supported for 15 minutes with 0.1M hydrochloric acid solution, then 5 ml/g of 30% (w/w) hydrogen peroxide was added and heated for 2 hours, and then heated for 2 hours at 300 W and 40 kHz conditions for 1 hour. After sonicating for a while, filtration and washing with 500 ml of purified water were repeated three times to extract Spongilla lacustris spicules.

After that, the extracted Spongilla lacustris spicule was supported in 0.5 M hydrochloric acid solution for 1 day, washed with phosphate buffered saline to neutralize acidity, washed 3 times with purified water, and dried at 50 ° C. I got my brother's Spongilla Lacustris Spicule.

Then, 20 ml/g of 35% (w/w) hydrogen peroxide was added to the needle-shaped Spongilla lacustris spicule, stirred and reacted for 15 hours, and pores ( pores) were formed. Thereafter, the process of filtration and washing with 500 ml of purified water was repeated three times, and then dried at 50° C. to obtain a needle-shaped Spongilla lacustris spicule with pores formed on the surface.

_{Calcium hydroxide (Ca(OH) 2} ) at a concentration of 5 N and magnesium hydroxide at a concentration of 5 N (Mg(OH) ₂ ) were added to the needle-shaped Spongilla lacustris spicule having pores on the surface 1: 10 ml/g of a basic compound mixed in a 0.5 volume ratio was added and reacted at 40° C. for 1 hour. Thereafter, the process of filtration and washing with 500 ml of purified water was repeated three times, and then dried at 50° C. to obtain a needle-shaped Spongilla lacustris spicule whose surface was modified to be hydrophilic (hydroxyl group).

<Examples and Comparative Examples>

Fine aggregate, coarse aggregate, and ultra-high-performance binder mixed in the components and contents shown in Table 1 below were put in a forced mixing mixer, mixed for 3 minutes under dry mixing conditions, and components and contents as shown in Table 1 below The ultra-high-performance modifier and water mixed with a high-performance modifier and water were simultaneously added and mixed for 2 minutes to prepare an ultra-high-performance, ultra-fast-hardening cement concrete composition and a comparative concrete composition.

Category (wt%) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 fine aggregate 39 39 39 39 39 coarse aggregate 33 33 33 33 33 water 3 3 3 3 3 Super high performance binder 18 18 18 18 18 (parts by weight) crude steel portland cement
(Powder: 4,720 ㎠/g) 100 100 100 100 100 Calcium sulfoaluminate 23 23 23 - 23 barium fluoride 12 12 12 - - Blast Furnace Slag Fine Powder 17 17 17 - 17 Ferronickel Slag ⁽¹⁾ 12 12 12 - 12 hollow activated carbon nanopowder 6
[Production Example 1] 6
[Production Example 2] 6
[Production Example 3] - - spicule 5
[Production Example 4] 5
[Production Example 5] 5
[Production Example 6] - - lepidochrosite
(Specific surface area: 77 g/m ² ) 2 2 2 - - hardening accelerator 1.4 1.4 1.4 1.4 1.4 setting retardant 0.2 0.2 0.2 0.2 0.2 water reducing agent 0.9 0.9 0.9 0.9 0.9 material separation inhibitor 0.5 0.5 0.5 0.5 0.5 Ultra high performance modifier 7 7 7 7 7 (parts by weight) Acrylic Latex ⁽²⁾ 100 100 100 100 100 Acrylonitrile-butadiene-styrene copolymer 35 35 35 - 35 polyvinyl acetate resin 38 38 38 - 38 aminomethyl polystyrene resin 19 19 19 - - silk fibroin 15 15 15 - - epigallocatechin gallate 3 3 3 - - oryzanol 3 3 3 - - Ceramide derivatives - One
[Formula 1-1] 1 ⁽³⁾ - - antifoam 0.8 0.8 0.8 0.8 0.8 air entrainment agent 1.2 1.2 1.2 1.2 1.2

[화학식 1-2]

⁽¹⁾ ferronickel slag: _{the content of SiO 2} is 54.8% by weight, the content of MgO is 34.2% by weight, the content of CaO is 0.9% by weight, the content of Fe ₂ O ₃ is 5.4% by weight, and Al ₂ O _{The content of 3} is 1.2 wt%, the content of NiO is 0.28 wt%, and _{the content of Cr 2} O ₃ is 0.54 wt%.

⁽²⁾ Acrylic latex: methyl methacrylate (MMA: Methyl Methacrylate) 45 wt%, acrylic acid normal butyl ester (BA: Butyl Acrylate Monomer) 8 wt%, acrylonitrile 4.5 wt%, dimethylammonoethylmethyl acrylate 3.5 Weight% and 2-ethylhexyl acrylate (2-EHA: 2-Ethyl Hexylacrylate) using the one prepared by polymerizing a monomer composition for polymerization containing 39% by weight.

^{(3) A} mixture of a ceramide-based derivative represented by the following Chemical Formula 1-1 and a ceramide-based derivative represented by the following Chemical Formula 1-2 is used in a 1:3 weight ratio
[Formula 1-1]

[Formula 1-2]

The following test examples are experiments comparing the properties of Examples 1 and 2 according to the present invention with those of Comparative Examples 1 and 2 in order to more easily understand the characteristics of Examples 1 to 3 according to the present invention disclosed above. the results are shown.

<Test Example 1>

A slump test (degree of kneading) was performed on the ultra-high performance super fast hardening cement concrete compositions according to Examples 1 to 3 of the present invention and the cement concrete compositions for comparison according to Comparative Examples 1 and 2 according to the method specified in KS F 2402. . The slump test is to test the quality of the dough, such as the softness and consistency of concrete, and the larger the number, the better the workability, that is, the workability when pouring concrete. The change value of the slump over time is shown in Table 2 below.

Slump (cm) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Immediately after stirring 25 25 25 25 25 after 20 minutes 22 23 24 21 22 after 30 minutes 16 17 19 13 15 after 40 minutes 13 15 17 5 9

As can be seen in Table 2, it was confirmed that the ultra-high performance super fast hardening cement concrete compositions according to Examples 1 to 3 were very excellent in workability compared to the comparative cement concrete compositions according to Comparative Examples 1 and 2 .

<Test Example 2>

In order to more specifically grasp the characteristics of the ultra-high performance super fast hardening cement concrete composition according to the present invention, the ultra high performance super fast hardening cement concrete compositions according to Examples 1 to 3 of the present invention and the comparative concrete compositions according to Comparative Examples 1 and 2 The characteristics were evaluated and the results are shown in Table 3 below.

Test Items Test Methods Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Drying shrinkage (length change rate (%)) KS F 2424 0.006 0.003 0.002 0.28 0.13 Compressive strength (MPa)_12 hours KS F 2405 27 30 33 14 18 Compressive strength (MPa)_28 days KS F 2405 39 41 42 22 28 Flexural strength (MPa)_12 hours KS F 2405 6.6 6.9 7.3 3.1 4.9 Flexural strength (MPa)_28 days KS F 2405 9.5 9.8 10.0 6.0 7.8 Adhesive strength (MPa)_12 hours KS F 2762 2.4 2.8 2.9 0.9 1.7 Adhesive strength (MPa)_28 days KS F 2762 3.5 3.8 4.1 1.7 2.5 Salt penetration resistance (coulomb) KS F 2711 714 681 617 1854 1192 Freeze-thaw resistance (%) KS F 2456 88 92 93 65 76 Wear resistance (mm) ASTM C 779 0.04 0.03 0.01 0.38 0.24 crack resistance AASHTO PP34-98 no cracks no cracks no cracks crack generation no cracks weight change rate
(%) Hydrochloric acid Japanese industrial standard draft
[Method of testing chemical resistance by solution immersion of concrete] -0.3 -0.3 0 -1.8 -0.9 sulfuric acid -0.02 0 -0.01 -0.8 -0.5 sodium hydroxide 0.2 0.1 0 1.3 0.7 Rust rate (%) KS F 2561 93.5 95.0 97.0 76.5 78.4 Absorption rate (%) KS F 4004 0.2 0.1 0.1 1.9 0.7

As can be seen in Table 3, the ultra-high performance super fast hardening cement concrete compositions according to Examples 1 to 3 had a small rate of change in length due to drying shrinkage compared to the comparative cement concrete compositions according to Comparative Examples 1 and 2 could check

In addition, the ultra-high performance super fast hardening cement concrete composition according to Examples 1 to 3 has superior compressive strength, flexural strength and adhesion strength, compared to the comparative cement concrete composition according to Comparative Example 1; It was confirmed that it had excellent salt penetration resistance, freeze-thaw resistance, abrasion resistance, chemical resistance, rust prevention rate and low water absorption.

As described above, those skilled in the art to which the present invention pertains will understand that the present invention may be implemented in other specific forms without changing the technical spirit or essential characteristics thereof. Therefore, it should be understood that all of the embodiments described above are illustrative and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention, rather than the above detailed description, all changes or modifications derived from the meaning and scope of the claims to be described later and their equivalents.

Claims (5)

20 to 50% by weight of fine aggregate, 10 to 40% by weight of coarse aggregate, 10 to 40% by weight of ultra high performance binder, 0.5 to 20% by weight of ultrahigh performance modifier and 0.1 to 5% by weight of water;
The ultra-high performance binder includes 100 parts by weight of crude steel portland cement, 20 to 40 parts by weight of calcium sulfoaluminate, 1 to 20 parts by weight of barium fluoride, 1 to 20 parts by weight of fine blast furnace slag powder, 1 to 20 parts by weight of ferronickel slag, hollow active 0.1 to 10 parts by weight of carbon nanopowder, 0.1 to 10 parts by weight of spicule, and 0.1 to 10 parts by weight of lepidocrosite;
The ultra-high performance modifier is 100 parts by weight of acrylic latex, 20 to 50 parts by weight of acrylonitrile-butadiene-styrene copolymer, 20 to 50 parts by weight of polyvinyl acetate resin, 10 to 30 parts by weight of aminomethyl polystyrene resin, 10 to 10 parts by weight of silk fibroin 30 parts by weight, 0.1 to 10 parts by weight of epigallocatechin gallate, and 0.1 to 10 parts by weight of oryzanol Ultra high performance super fast hardening cement concrete composition, characterized in that it contains.
According to claim 1,
The hollow activated carbon nanopowder is a hollow activated carbon nanopowder having crystals of metal sulfide on the surface;
The hollow activated carbon nanopowder having crystals of metal sulfide on the surface is
preparing a first electrospinning solution by dissolving a metal precursor, a sulfur salt, polycarbonate (PC) and peroxyacetyl nitrate (PAN) in a first solvent;
preparing a second electrospinning solution by dissolving polymethyl methacrylate (PMMA, Polymethyl methacrylate) in a second solvent;
preparing a dual nozzle having the same axis as the outer nozzle and the inner nozzle, connecting the first electrospinning solution to the outer nozzle, and connecting the second electrospinning solution to the inner nozzle for electrospinning;
A core in which a metal precursor, sulfur salt, and a first polymer are present in a shell portion formed by electrospinning through the outer nozzle, and a second polymer is present in a core portion formed by electrospinning through the inner nozzle - Forming a shell-shaped composite;
pulverizing the core-shell-shaped composite to form a core-shell-shaped composite nanopowder; and
Heat treatment of the core-shell composite nanopowder in a reducing or inert atmosphere for thermal decomposition of the core part composed of the second polymer in the core-shell composite nanopowder, carbonization of the polymer of the shell part, and crystallization of metal sulfide An ultra-high performance super fast hardening cement concrete composition, characterized in that it is prepared by a manufacturing method comprising the steps of.
3. The method of claim 2,
The metal precursor is
Iron (II) acetylacetonate (Fe(acac) ₂ ), iron (III) acetylacetonate (Fe (acetylacetonate) ₃ ), iron (II) acetate (Fe(ac) ₂ ), iron (III) acetate (Fe (ac) ₃ ), iron sulfamate (Fe(NH ₂ SO ₃ ) ₂ ), iron(II) stearate, iron(III) stearate, iron(II) laurate, iron(III) laurate, iron(II) oleate ), iron (III) oleate, and at least one iron precursor selected from the group consisting of mixtures thereof;
Copper acetate, copper acetylacetonate, copper i-butyrate, copper ethylacetoacetate, copper 2-ethylhexanoate, copper At least one copper precursor selected from the group consisting of gluconate, copper methoxide, copper neodecanoate, tetraaminecopper sulfate hydrate, and mixtures thereof A mixture of 1: 0.5 to 1 by weight was used;
The metal sulfide is an ultra-high performance super fast hardening cement concrete composition, characterized in that it includes iron sulfide and copper sulfide.
According to claim 1,
The spicule is a needle-shaped Spongilla lacustris spicule whose surface is modified to be hydrophilic;
The needle-shaped Spongilla lacustris spicule, whose surface is modified to be hydrophilic, is
Supporting the crushed Spongilla lacustris in hydrochloric acid solution, and then heating and sonicating by adding hydrogen peroxide to extract Spongilla lacustris spicules;
After supporting the extracted Spongilla lacustris spicules in hydrochloric acid solution, washing with phosphate buffered saline to neutralize the acidity and drying to obtain needle-shaped Spongilla lacustris spicules;
reacting the needle-shaped Spongilla lacustris spicule and hydrogen peroxide for 6 to 20 hours to form pores on the surface of the needle-shaped Spongilla lacustris spicule; and
Super high performance super fast hardening cement concrete, characterized in that it is manufactured by a manufacturing method comprising the step of modifying the surface to be hydrophilic by reacting a basic compound with a needle-shaped Spongilla lacustris spicule having pores formed on the surface composition.
A method of repairing concrete structures for roads and bridges using the ultra-high performance super fast hardening cement concrete composition according to any one of claims 1 to 4,
removing the deteriorated, damaged or contaminated parts of road and bridge concrete structures; cleaning the removed area; Primer or blooming treatment on the cleaned area; pouring the ultra-high-performance super-fast hardening cement concrete composition on the primer or blooming-treated top; After pouring, the step of tinting in order to increase the crack induction and slip resistance; Spraying a curing agent to prevent initial plastic cracking by preventing evaporation of moisture in the upper part after the tinting step; and curing the road and bridge concrete structures.