KR102414943B1 - Shrinkage-reducing ultra high early strength and early strength cement concrete composition and repairing method for road pavement using the same - Google Patents

Abstract

상기 식에서,
R¹은 탄소수 1 내지 6의 알킬 또는 (탄소수 1 내지 6의 알킬)아민이고,
R²는 (탄소수 1 내지 6의 알킬)아미노(탄소수 1 내지 6의 알킬)아민 또는 피페리디닐 (탄소수 1 내지 6의 알킬)아민이고,
X는 F 또는 Cl이다.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 a functional improving binder, 0.5 to 20% by weight of a functional improving admixture, and 0.1 to 5% by weight of water;
The function-improving 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 potassium nickel cobalt fluoride, 1 to 20 parts by weight of fine blast furnace slag powder, 0.1 to 10 parts by weight of ladle slag, oxidized 0.1 to 10 parts by weight of tin, 0.1 to 10 parts by weight of potassium hexafluoromanganate, and 0.1 to 10 parts by weight of spicule;
The function-improving admixture is 100 parts by weight of acrylic latex, 70 to 90 parts by weight of polymethyl methacrylate-(adamantyl) acrylate copolymer, 50 to 70 parts by weight of hydroxyfluorine (meth)acrylate, and Formula 1 below. By using a compound containing 10 to 30 parts by weight of the indicated 2-thio-4-amino pyrimidine derivative, 0.1 to 10 parts by weight of bio-heavy oil, 0.1 to 10 parts by weight of limocitrin, and 0.1 to 10 parts by weight of apigenin;
It is possible to secure early strength and improve physical properties such as strength, as well as prevent initial cracking and expansion fracture, as well as shrinkage-reducing early steel and crude steel cement concrete composition with greatly improved properties required for pavement and the same It relates to the road pavement maintenance and repair method used.
[Formula 1]

In the above formula,
R ¹ is alkyl having 1 to 6 carbon atoms or (alkyl having 1 to 6 carbon atoms)amine,
R ² is (alkyl having 1 to 6 carbons)amino(alkyl of 1 to 6 carbons)amine or piperidinyl (alkyl of 1 to 6 carbons)amine,
X is F or Cl.

Description

Shrinkage-reducing ultra high early strength and early strength cement concrete composition and repairing method for road pavement using the same}

According to the present invention, it is possible to secure early strength and improve physical properties such as strength, as well as prevent initial cracking and expansion and fracture phenomena, as well as reducing shrinkage type steel and crude steel cement concrete with greatly improved properties required for pavement. It relates to a composition and a road pavement maintenance method using the same.

Concrete pavement is poured through a bi-beam process in accordance with the mixing design (cement, coarse aggregate, sand, water), and has the advantage of expressing the strength of the material and its adhesion.

However, the disadvantages are that the construction restrictions for temperature and surrounding environment are large, the curing period is long, cracking due to drying and shrinkage is easy to occur, and laitance is generated on the surface due to bleeding, so the surface strength is weak and the durability is lowered. have. Moreover, due to the above-mentioned disadvantages, when the reinforcing bars inside the concrete are corroded, the volume expands, which may lead to cracks and cross-section loss of the concrete structure. More specifically, cracks in concrete can be caused by various factors such as external environmental causes such as salt damage and deterioration, material properties such as design load, plastic shrinkage or drying shrinkage, mixing conditions, and constructional factors. Concrete expands due to these deterioration factors and eventually the cross section falls off, which can cause collapse of concrete structures because they do not fully exhibit their original performance.

In order to overcome the disadvantages of the conventional concrete pavement, recently, SBR (Styrene) is applied to concrete to reduce vehicle control time and construction cost by quickly repairing damaged parts of concrete due to its fast curing rate, and to express rapid structural strength. -Butadiene Rubber) Latex Modified Concrete that forms a watertight structure by adding latex has been developed and used.

However, latex had a limit in maintaining the required adhesion strength with spherical concrete that had undergone deterioration or neutralization, and had poor chloride penetration resistance or freeze-thaw stability in winter, resulting in surface peeling, partial damage and dropping, porthole generation and drying shrinkage after winter. The problem of cracking due to relaxation stress still remained.

Republic of Korea Patent Registration No. 10-1547895 Republic of Korea Patent Registration No. 10-1760230 Republic of Korea Patent Registration No. 10-1547895

The present invention has been devised to solve the above-mentioned problems, and one embodiment of the present invention enables early strength to be secured, so it is possible to quickly repair the damaged part of concrete, and to realize excellent adhesion performance with the existing bridge pavement. At the same time, it is possible to prevent initial cracking and expansion fracture, as well as reduced shrinkage type steel and crude steel cement concrete composition with improved chloride penetration resistance, freeze-thaw resistance according to temperature change and crack resistance, and road pavement maintenance using the same It is intended to provide a technique.

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 a functional improvement binder, 0.5 to 20% by weight of a functional improving admixture, and 0.1 to 5% by weight of water;

The function-improving 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 potassium nickel cobalt fluoride, 1 to 20 parts by weight of fine blast furnace slag powder, 0.1 to 10 parts by weight of ladle slag, oxidized 0.1 to 10 parts by weight of tin, 0.1 to 10 parts by weight of potassium hexafluoromanganate, and 0.1 to 10 parts by weight of spicule;

The function-improving admixture is 100 parts by weight of acrylic latex, 70 to 90 parts by weight of polymethyl methacrylate-(adamantyl) acrylate copolymer, 50 to 70 parts by weight of hydroxyfluorine (meth)acrylate, and Formula 1 below. The indicated 2-thio-4-amino pyrimidine derivative 10 to 30 parts by weight, 0.1 to 10 parts by weight of bio-heavy oil, 0.1 to 10 parts by weight of rimocitrin, and 0.1 to 10 parts by weight of apigenin. Steel and crude steel cement concrete compositions are provided.

[Formula 1]

In the above formula,

R ¹ is alkyl having 1 to 6 carbon atoms or (alkyl having 1 to 6 carbon atoms)amine,

R ² is (alkyl having 1 to 6 carbons)amino(alkyl of 1 to 6 carbons)amine or piperidinyl (alkyl of 1 to 6 carbons)amine,

X is F or Cl.

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.

The basic compound may be a mixture of 3 to 7 N concentration of calcium hydroxide (Ca(OH) ₂ ) and 3 to 7 N concentration of magnesium hydroxide (Mg(OH) ₂ ) in a volume ratio of 1: 0.1 to 0.5.

The bio-heavy oil is liquefied by heating at least one type of waste oil selected from the group consisting of animal waste hog, animal waste tallow, sewage oil residue, and mixtures thereof at a temperature of 40 to 50 ° C., followed by filtration to remove solids. to do; After removing the moisture by contacting the filtered liquefied waste oil with magnesium and anhydrous sodium sulfate (Na ₂ SO ₄ ), pretreatment by filtration; preparing a raw material mixture by mixing the pre-treated liquefied waste oil and 70 to 95% by weight of an aqueous alcohol solution solvent in a 1:0.1 to 0.5 weight ratio; and reacting the raw material mixture at a temperature of 200 to 600° C. and a pressure of 100 to 250 bar, which is a supercritical state of the alcohol aqueous solvent, to prepare bio-heavy oil.

In addition, another embodiment of the present invention is a road pavement maintenance and repair method using the shrinkage-reducing ultra-fine steel and crude steel cement concrete composition,

removing the deteriorated, damaged or contaminated portion of the construction target surface; cleaning the removed area; Primer or blooming treatment on the cleaned area; pouring the shrinkage-reducing super-strength steel and crude-strength cement concrete composition on the primer or blooming-treated upper part; 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 road pavement maintenance method comprising the step of curing.

According to the shrinkage-reducing early steel and crude steel cement concrete composition and the road pavement maintenance method using the same according to an embodiment of the present invention, it is possible to secure early strength after application by greatly improving the curing speed of the mortar, and thus the construction period is greatly shortened. It has the effect of shortening and minimizing the traffic control time. In addition, by promoting the initial hydration of cement and densification of the tissue, physical properties such as excellent adhesion to existing bridge pavements, flexural strength, tensile strength and compressive strength are improved, and the initial cracking and expansion fracture phenomena are prevented due to excellent shrinkage reduction effect. has a preventive effect. In addition, all properties required for pavement, such as watertightness, adhesion, chemical resistance, waterproofness, rust prevention, neutralization resistance, chloride penetration resistance, freeze-thaw resistance and crack resistance due to temperature change, are greatly improved, so the repair effect of concrete structures has an effect that can be maintained for a long time.

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 a functional improvement binder, 0.5 to 20% by weight of a functional improving admixture, and 0.1 to 5% by weight of water;

The function-improving 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 potassium nickel cobalt fluoride, 1 to 20 parts by weight of fine blast furnace slag powder, 0.1 to 10 parts by weight of ladle slag, oxidized 0.1 to 10 parts by weight of tin, 0.1 to 10 parts by weight of potassium hexafluoromanganate, and 0.1 to 10 parts by weight of spicule;

The function-improving admixture is 100 parts by weight of acrylic latex, 70 to 90 parts by weight of polymethyl methacrylate-(adamantyl) acrylate copolymer, 50 to 70 parts by weight of hydroxyfluorine (meth)acrylate, and Formula 1 below. The indicated 2-thio-4-amino pyrimidine derivative 10 to 30 parts by weight, 0.1 to 10 parts by weight of bio-heavy oil, 0.1 to 10 parts by weight of rimocitrin, and 0.1 to 10 parts by weight of apigenin. Steel and crude steel cement concrete compositions are provided.

[Formula 1]

In the above formula,

R ¹ is alkyl having 1 to 6 carbon atoms or (alkyl having 1 to 6 carbon atoms)amine,

R ² is (alkyl having 1 to 6 carbons)amino(alkyl of 1 to 6 carbons)amine or piperidinyl (alkyl of 1 to 6 carbons)amine,

X is F or Cl.

According to the shrinkage-reducing early steel and crude steel cement concrete composition according to an embodiment of the present invention and the road pavement maintenance method using the same, the curing speed of the mortar is significantly improved to secure early strength after application, and the construction period is shortened. It has the effect of significantly shortening and minimizing the traffic control time. In addition, by promoting the initial hydration of cement and densification of the tissue, physical properties such as excellent adhesion to existing bridge pavements, flexural strength, tensile strength and compressive strength are improved, and the initial cracking and expansion fracture phenomena are prevented due to excellent shrinkage reduction effect. has a preventive effect. In addition, all properties required for pavement, such as watertightness, adhesion, chemical resistance, waterproofness, rust prevention, neutralization resistance, chloride penetration resistance, freeze-thaw resistance and crack resistance due to temperature change, are greatly improved, so the repair effect of concrete structures has an effect that can be maintained for a long time.

The shrinkage-reducing early steel and crude steel 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 functional improvement binder, and 0.5 to 20% by weight of functional improving admixture. % and 0.1 to 5% by weight of water.

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 shrinkage reduction type initial steel and crude steel cement concrete composition of the present invention, and the coarse aggregate is 10 to 40 weight% based on the shrinkage reduction type initial steel and crude steel cement concrete composition of the present invention % is preferred.

The function-improving binder used in the present invention is preferably contained in an amount of 10 to 40% by weight based on the shrinkage-reducing type initial steel and crude steel cement concrete composition of the present invention. When the content of the functional improvement binder is too small, the possibility of insufficient viscosity and bleeding may increase, and thus the possibility of occurrence of plastic cracks may also increase. In addition, the permeability resistance may decrease due to deterioration of the strength and watertightness of concrete. In addition, when the content of the functional improvement binder is too large, the viscosity increases, workability decreases, it becomes difficult to control the pot life, the initial strength decreases, and the long-term strength continues to increase due to excessive watertightness increase, so that concrete structures and pavements Dry shrinkage cracking of the sieve may occur.

The function-improving 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 potassium nickel cobalt fluoride, 1 to 20 parts by weight of fine blast furnace slag powder, 0.1 to 10 parts by weight of ladle slag, oxidized 0.1 to 10 parts by weight of tin, 0.1 to 10 parts by weight of potassium hexafluoromanganate, and 0.1 to 10 parts by weight of spicule 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 functional improvement 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. When 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 potassium nickel cobalt fluoride functions to improve not only excellent strength properties, but also excellent shrinkage reduction effect, abrasion resistance, water resistance, waterproofness, chemical resistance and freeze-thaw resistance.

By using such a potassium nickel cobalt fluoride having a hollow spherical perovskite crystal, it is possible to further improve the above-described effect, and, in particular, has an effect of greatly improving an excellent shrinkage reduction effect and abrasion resistance.

More specifically, for potassium nickel cobalt fluoride having a perovskite crystal in the hollow spherical shape, 1 to 5 mole ratios of the nickel precursor and 10 to 50 mole ratios of ammonium fluoride are dissolved in a solvent, and then 5 to 20 moles of potassium fluoride sequentially preparing a mixed solution by dissolving the ratio and 1 molar ratio of the cobalt precursor; heat-treating the mixed solution at a temperature of 100 to 200° C. for 15 to 30 hours; and recovering the precipitate from the mixed solution on which the heat treatment has been completed; Those having an average particle diameter of 200 to 600 nm and having a composition of KNi _1-x Co _x F _3-δ (0 < x < 1, 0.1 < δ < 0.5) may be more preferably used.

In this case, the nickel precursor is at least one selected from the group consisting of nickel nitrate, nickel acetate, nickel chloride, nickel sulfate, hydrates thereof, and mixtures thereof. can be used; The cobalt precursor may be one or more selected from the group consisting of cobalt nitrate, cobalt chloride, cobalt acetate, cobalt sulfate, hydrates thereof, and mixtures thereof. can

In addition, the solvent is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol hexylene glycol, 1,2-hexadecanediol (1,2-hexadecanediol) And at least one glycol solvent selected from the group consisting of mixtures thereof; or methyl glycol, butyl glycol, butyl triglycol, butyl polyglycol, hexyl glycol, hexyl diglycol, ethylhexyl glycol, ethylhexyl diglycol, aryl glycol, phenyl glycol, phenyl diglycol, benzyl glycol, methyl propylene glycol, methyl propylene One or more glycol ethers selected from the group consisting of diglycol, methyl propylene triglycol, propyl propylene glycol, propyl propylene diglycol, butyl propylene glycol, butyl propylene diglycol, phenyl propylene glycol, methyl propylene glycol acetate, and mixtures thereof A solvent may be used.

The potassium fluoride nickel cobalt 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 potassium nickel cobalt fluoride is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the potassium nickel cobalt fluoride is too large, there is a problem that the curing rate may be reduced.

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 ladle slag refers to slag generated in a converter or ladle generated during the steelmaking process, and is an industrial by-product having a component similar to that of general cement, and can undergo a hydration reaction to form C-S-H gel similar to cement. Thereby, it improves stable long-term strength expression and water tightness, provides microcrack prevention and shrinkage prevention effect by lowering the heat of hydration, and improves chemical durability to provide excellent salt damage and freeze-thaw resistance.

More specifically, the ladle slag is silicon oxide (SiO ₂ ) 18.2 to 19.9 wt%, aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) 10.1 to 11.4 wt%, iron oxide (Fe ₂ O ₃ ) 7.1 to 8.0 wt%, oxide Calcium (CaO) 42.0 to 43.3 wt%, magnesium oxide (MgO) 0.8 to 2.5 wt%, sulfur trioxide (SO ₃ ) 2.6 to 4.5 wt%, sodium oxide (Na ₂ O) 0.1 to 1.0 wt%, potassium oxide (K ₂ ) O) 0.1 to 0.8% by weight, sulfur (S) 0.5 to 2.4% by weight, iron (Fe) 5.9 to 6.9% by weight, and phosphorus (P) containing 0.2 to 1.3% by weight may be more preferably used, and the fineness A value of 3,000 to 7,500 cm 2 /g may be preferably used.

The ladle slag is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the crude steel portland cement. When the content of the ladle slag is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the ladle slag is too large, there is a problem that the initial strength expression may be delayed.

The tin oxide functions to improve chemical resistance, weather resistance, salt damage and freeze-thaw resistance, and to provide heat resistance, abrasion resistance, crack prevention and shrinkage prevention effects along with an excellent strength expression effect.

The tin oxide is hydroxyapatite-coated porous tin dioxide (SnO ₂ ) by using it, and not only can further improve the above-described effects, but, in particular, excellent chemical resistance, weather resistance, salt damage and freeze-thaw resistance, It has the effect of greatly improving the effect of preventing cracks and preventing shrinkage.

More specifically, the hydroxyapatite-coated porous tin dioxide (SnO ₂ ) is sodium nitrate (NaNO ₃ ) and tin chloride (SnCl ₂ ) in distilled water in a 1: 1 to 2 weight ratio by adding and mixing to form a mixture step; After evaporating the mixture at a temperature of 75 to 95 ° C. sodium nitrate (NaNO ₃ ), Sn(NO ₃ ) ₂ , preparing a first complex comprising sodium chloride (NaCl); Heating the first complex at a temperature of 400 to 600 ° C. to prepare a second complex comprising sodium nitrate (NaNO ₃ ), tin dioxide (SnO ₂ ), and sodium chloride (NaCl); Washing the second composite to prepare tin dioxide (SnO ₂ ) nanoparticles having a porous structure; mixing the tin dioxide (SnO ₂ ) nanoparticles of the porous structure with hydroxyapatite sol to form a hydroxyapatite sol coating layer on all or part of the surface of the tin dioxide (SnO ₂ ) nanoparticles of the porous structure; and heat-treating the porous tin dioxide (SnO ₂ ) on which the hydroxyapatite sol coating layer is formed at a temperature of 650 to 950 ° C. to prepare porous tin dioxide (SnO ₂ ) coated with hydroxyapatite; It can be preferably used that is prepared with.

The sodium nitrate (NaNO ₃ ), tin dioxide (SnO ₂ ), and washing a second complex containing sodium chloride (NaCl) to prepare tin dioxide (SnO ₂ ) nanoparticles having a porous structure; is sodium nitrate (NaNO ₃ ) ) and sodium chloride (NaCl) are dissolved in distilled water, so that the second complex can be washed with distilled water through a vacuum pump.

In this case, the above-described effect may be further improved by using a hydroxyapatite sol in which Si is substituted as the hydroxyapatite sol.

More specifically, the Si-substituted hydroxyapatite sol is triethylphosphite (TEP) at a molar concentration of 0.5 to 0.8 molar concentration (mol/L) and tetraethyl orthosilicate at a molar concentration of 0.1 to 0.5 molar concentration (mol/L) ( TEOS) in ethyl alcohol is titrated to pH 2 with 0.1N hydrochloric acid, followed by stirring at 30 to 60° C. for 4 to 7 hours to hydrolyze the TEOS-TEP solution; A solution of 1.5 to 2 molar concentration (mol/L) of calcium nitrate tetrahydrate in ethyl alcohol, mixing the hydrolyzed TEOS-TEP solution drop by drop in the same volume ratio; and stirring the mixture obtained in the above step at 30 to 60° C. for 4 to 7 hours.

The tin oxide 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 tin oxide is too small, there is a problem that the above-mentioned improvement effect may be insufficient, and when the content of the tin oxide is too large, the manufacturing cost increases and the price competitiveness may decrease.

The potassium hexafluoromanganate 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 potassium hexafluoromanganate 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 potassium hexafluoromanganate is too small, there is a problem that the above-described improvement effect may be insufficient. There is a problem that can be degraded.

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.

In addition, the functional improvement 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 function-improving admixture functions to improve the curing time, workability, strength and durability of the shrinkage-reducing type ultra-fine steel and crude steel cement concrete composition of the present invention.

The function-improving admixture is preferably contained in an amount of 0.5 to 20% by weight in the shrinkage-reducing type crude steel and crude steel cement concrete composition of the present invention. When the content of the function-improving admixture is too small, the improvement effect may be weak, and when the content of the function-improving admixture is too large, the viscosity is lowered and 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 function-improving admixture is 100 parts by weight of acrylic latex, 70 to 90 parts by weight of polymethyl methacrylate-(adamantyl) acrylate copolymer, 50 to 70 parts by weight of hydroxyfluorine (meth)acrylate, and Formula 1 below. A compound containing 10 to 30 parts by weight of the indicated 2-thio-4-amino pyrimidine derivative, 0.1 to 10 parts by weight of bio-heavy oil, 0.1 to 10 parts by weight of limocitrin, and 0.1 to 10 parts by weight of apigenin may be used.

[Formula 1]

In the above formula,

R ¹ is alkyl having 1 to 6 carbon atoms or (alkyl having 1 to 6 carbon atoms)amine,

R ² is (alkyl having 1 to 6 carbons)amino(alkyl of 1 to 6 carbons)amine or piperidinyl (alkyl of 1 to 6 carbons)amine,

X is F or Cl.

The acrylic latex serves to improve water resistance, alkali resistance, and weather resistance as well as improving bending, tensile and adhesion strength with excellent adhesion.

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 functional improvement admixture is based on 100 parts by weight of the acrylic latex.

The polymethyl methacrylate-(adamantyl) acrylate copolymer functions to enhance warpage, tensile and adhesive strength. In addition, it prevents material separation, improves tensile strength, suppresses cracking, reduces the width of cracks after cracks occur, improves durability, and improves weather resistance.

The polymethyl methacrylate-(adamantyl) acrylate copolymer is preferably contained in an amount of 70 to 90 parts by weight based on 100 parts by weight of the acrylic latex. When the content of the polymethyl methacrylate-(adamantyl) acrylate copolymer is too small, there is a problem that the improvement effect may be reduced, and the polymethyl methacrylate-(adamantyl) acrylate When the content of the copolymer is too large, the above-mentioned improvement effect is not improved any more, there is a problem in that price competitiveness may be lowered.

The hydroxyfluorine (meth)acrylate functions to improve bending, tensile and adhesion strength, and to provide excellent waterproof and water resistance. In addition, it is possible to prevent material separation and to suppress the occurrence of cracks caused by temperature deformation and self-shrinkage deformation of concrete caused by hydration of cement. It functions to improve weather resistance.

These hydroxyfluorine (meth) acrylates are 3- (perfluorobutyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluorohexyl) -2-hydroxypropyl (meth) acrylate, 3- At least one selected from the group consisting of (perfluorooctyl)-2-hydroxypropyl (meth)acrylate and mixtures thereof may be preferably used.

The hydroxyfluorine (meth)acrylate is preferably contained in an amount of 50 to 70 parts by weight based on 100 parts by weight of the acrylic latex. When the content of the hydroxyfluorine (meth)acrylate is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the hydroxyfluorine (meth)acrylate is too large, workability and price competitiveness There is a problem that this can be degraded.

The 2-thio-4-amino pyrimidine derivative represented by Formula 1 provides excellent workability and excellent miscibility between materials, improves crack resistance, resistance to salt damage, neutralization, etc. and durability, and shortens curing time. function that can.

The 2-thio-4-amino pyrimidine derivative represented by Formula 1 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 2-thio-4-amino pyrimidine derivative is too small, there is a problem that the improvement effect may be reduced, and when the content of the 2-thio-4-amino pyrimidine derivative is too large The above-mentioned improvement effect is no longer improved, and there is a problem in that price competitiveness may be lowered, or strength and durability may be lowered.

The bio heavy oil functions to improve waterproofness, water resistance and workability. In particular, it can effectively suppress the occurrence of cracks, and after cracks occur, the width of cracks is reduced to improve durability and improve weather resistance.

The bio-heavy oil is obtained by heating one or more waste oils and fats selected from the group consisting of animal waste hogs, animal waste tallow, sewage oil residues, and mixtures thereof at a temperature of 40 to 50 ° C. removing; After removing the moisture by contacting the filtered liquefied waste oil with magnesium and anhydrous sodium sulfate (Na ₂ SO ₄ ), pretreatment by filtration; preparing a raw material mixture by mixing the pre-treated liquefied waste oil and 70 to 95% by weight of an aqueous alcohol solution solvent in a 1:0.1 to 0.5 weight ratio; and reacting the raw material mixture at a temperature of 200 to 600° C. and a pressure of 100 to 250 bar, which is a supercritical state of the aqueous alcohol solvent, to prepare bio-heavy oil. can

At this time, the alcohol of the alcohol aqueous solution solvent is not particularly limited as long as it is an alcohol commonly used in the art, but for example, methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutanol, 2-butanol, tert-butanol, n-pentanol, isopentyl alcohol, 2-methyl-1-butanol, neopentyl alcohol, diethyl kevinol, methyl propyl kevinol, methyl isopropyl kevinol, dimethyl ethyl kevinol, 1-hexanol, 2-hexane Ol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentane ol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 2 ,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol and mixtures thereof One or more selected from the group consisting of may be used. More preferably, a mixture of ethanol and methyl propyl kebinol in a volume ratio of 1: 0.3 to 0.7 may be used.

The bio-heavy oil is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic latex. If the content of the bio-heavy oil is too small, the improvement effect may be insufficient, and if the content of the bio-heavy oil is too large, the strength and durability may be reduced.

The limocitrin functions to provide excellent workability and excellent miscibility between materials, and to improve durability such as resistance to salt damage, neutralization, and frost damage, water permeability resistance, chemical resistance, waterproofness, and rust prevention.

The limocitrin 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 limocitrin is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of limocitrin is too large, there is a problem that the initial strength expression is delayed or price competitiveness may be lowered.

The apigenin functions to provide excellent workability and excellent miscibility between materials, and to improve resistance to salt damage and neutralization.

The apigenin 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 apigenin is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of apigenin is too large, there is a problem that the initial strength expression is delayed or price competitiveness may be lowered.

In addition, the function-improving admixture is an additive generally used in the art, and may further include at least one 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 shrinkage-reduced initial steel and crude steel cement concrete composition according to a preferred embodiment of the present invention comprises 20 to 50 wt% of fine aggregate, 10 to 40 wt% of coarse aggregate, and 10 to 40 wt% of functional improvement binder after stirring in a forced mixer, It can be prepared by further mixing 0.5 to 20% by weight of the functional improvement admixture and 0.1 to 5% by weight of water and stirring for a predetermined time (eg, 1 to 10 minutes).

In addition, another embodiment of the present invention is a road pavement maintenance and repair method using the shrinkage-reducing ultra-fine steel and crude steel cement concrete composition,

removing the deteriorated, damaged or contaminated portion of the construction target surface; cleaning the removed area; Primer or blooming treatment on the cleaned area; pouring the shrinkage-reducing ultra-strength steel and crude steel cement concrete composition on the primer or blooming-treated upper portion; 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 it provides a road pavement maintenance method comprising the step of curing.

More specifically, the step of removing the deteriorated, damaged, or contaminated portion of the construction target surface; cutting and blasting the deteriorated, damaged or contaminated portion of the construction target surface using a crusher, planer, shot blaster, or water jet. can be performed.

In addition, the step of treating the cleaned area with a primer or blooming; may be used to refer to an operation of facilitating adhesion of the shrinkage-reducing early steel and crude steel cement concrete composition according to an embodiment of the present invention to the construction target surface. have.

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 shrinkage-reducing early steel and crude steel cement concrete composition and the road pavement maintenance method using the same according to an embodiment of the present invention, it is possible to secure early strength after application by greatly improving the curing speed of the mortar, and thus the construction period is greatly shortened. It has the effect of shortening and minimizing the traffic control time. In addition, by promoting the initial hydration of cement and densification of the tissue, physical properties such as excellent adhesion to existing bridge pavements, flexural strength, tensile strength and compressive strength are improved, and the initial cracking and expansion fracture phenomena are prevented due to excellent shrinkage reduction effect. has a preventive effect. In addition, all properties required for pavement, such as watertightness, adhesion, chemical resistance, waterproofness, rust prevention, neutralization resistance, chloride penetration resistance, freeze-thaw resistance and crack resistance due to temperature change, are greatly improved, so the repair effect of concrete structures has an effect that can be maintained for a long time.

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 potassium fluoride nickel cobalt having perovskite crystals

A 4 molar ratio of nickel nitrate hexahydrate was first dissolved in ethylene glycol and stirred for 1 hour. Thereafter, 15 molar ratios of potassium fluoride dihydrate and 1 molar ratio of cobalt nitrate tetrahydrate were dissolved and stirred for about 10 minutes to prepare a mixed solution. Then, the mixed solution was transferred to a Teflon-lined stainless steel autoclave and heat-treated at a temperature of 180° C. for 20 hours. Thereafter, the heat-treated mixed solution was cooled to room temperature, and the precipitate was collected by centrifugal filtration, washed with ethanol several times, and dried at 60° C. for 12 hours.

Thus, potassium nickel cobalt fluoride having a form of agglomerated powder having a composition of KNi _0.8 Co _0.2 F _2.8 was prepared.

<Preparation Example 2>

Preparation of potassium fluoride nickel cobalt having a hollow spherical perovskite crystal

4 mole ratio of nickel nitrate hexahydrate and 40 mole ratio of ammonium fluoride were first dissolved in ethylene glycol and stirred for 1 hour. Thereafter, 15 mole ratios of potassium fluoride dihydrate and 1 mole ratio of cobalt nitrate tetrahydrate were dissolved and stirred for about 10 minutes to prepare a mixed solution. Then, the mixed solution was transferred to a Teflon-lined stainless steel autoclave and heat-treated at a temperature of 180° C. for 20 hours. Thereafter, the heat-treated mixed solution was cooled to room temperature, and the precipitate was collected by centrifugal filtration, washed with ethanol several times, and dried at 60° C. for 12 hours.

Thus, potassium nickel cobalt fluoride having an average particle diameter of about 471 nm and a hollow spherical perovskite crystal having a composition of KNi _0.8 Co _0.2 F _2.8 was prepared.

<Production Example 3>

Porous tin dioxide (SnO ₂ ) Produce

Sodium nitrate (NaNO ₃ ) and tin chloride (SnCl ₂ ) in distilled water were added in a 1: 1.7 weight ratio and mixed to form a mixture; After evaporating the water at a temperature of 85 ℃ the mixture, sodium nitrate (NaNO ₃ ), Sn(NO ₃ ) ₂ , a first complex including sodium chloride (NaCl) was prepared. Thereafter, the first complex was heat-treated at a temperature of 550° C. to prepare a second complex including sodium nitrate (NaNO ₃ ), tin dioxide (SnO ₂ ), and sodium chloride (NaCl). Then, by washing and drying the second composite with distilled water, tin dioxide (SnO ₂ ) nanoparticles having a porous structure were prepared.

<Production Example 4>

Hydroxyapatite coated porous tin dioxide (SnO ₂ ) Produce

Sodium nitrate (NaNO ₃ ) and tin chloride (SnCl ₂ ) in distilled water were added in a 1: 1.7 weight ratio and mixed to form a mixture; After evaporating the water at a temperature of 85 ℃ the mixture, sodium nitrate (NaNO ₃ ), Sn(NO ₃ ) ₂ , a first complex including sodium chloride (NaCl) was prepared. Thereafter, the first complex was heat-treated at a temperature of 550° C. to prepare a second complex including sodium nitrate (NaNO ₃ ), tin dioxide (SnO ₂ ), and sodium chloride (NaCl). Then, by washing and drying the second composite with distilled water, tin dioxide (SnO ₂ ) nanoparticles having a porous structure were prepared. After mixing the tin dioxide (SnO ₂ ) nanoparticles of the porous structure with hydroxyapatite sol to form a hydroxyapatite sol coating layer on all or part of the surface of the tin dioxide (SnO ₂ ) nanoparticles of the porous structure; The porous tin dioxide (SnO ₂ ) on which the hydroxyapatite sol coating layer was formed was heat-treated at a temperature of 800° C. to prepare porous tin dioxide (SnO ₂ ) coated with hydroxyapatite.

At this time, the hydroxyapatite sol is obtained by titrating a solution of triethylphosphite (TEP) of 1.5 molar concentration (mol/L) in ethyl alcohol to a pH of 2 with 0.1N hydrochloric acid, and then at 50° C. for 6 hours. After stirring to hydrolyze the TEP solution; A solution of 1.8 molar concentration (mol/L) of calcium nitrate tetrahydrate in ethyl alcohol was mixed with the hydrolyzed TEP solution dropwise at the same volume ratio. Thereafter, the mixture prepared in the above step was used by stirring at 45° C. for 5 hours.

<Preparation Example 5>

Si-substituted hydroxyapatite-coated porous tin dioxide (SnO ₂ ) Produce

In the same manner as in Preparation Example 2, hydroxyapatite-coated porous tin dioxide (SnO ₂ ) was prepared; Instead of the hydroxyapatite sol, Si-substituted hydroxyapatite sol was used.

At this time, the Si-substituted hydroxyapatite sol was obtained by mixing triethylphosphite (TEP) at a molar concentration of 0.7 (mol/L) and tetraethyl orthosilicate (TEOS) at a molar concentration of 0.3 (mol/L) in ethyl alcohol. After titrating the solution dissolved in 0.1N hydrochloric acid to pH 2 and stirring at 50 °C for 6 hours to hydrolyze the TEOS-TEP solution; 1.8 molar concentration (mol/L) of calcium nitrate tetrahydrate (calcium nitrate tetrahydrate) was dissolved in ethyl alcohol, the hydrolyzed TEOS-TEP solution was mixed drop by drop in the same volume ratio. Thereafter, the mixture prepared in the above step was used by stirring at 45° C. for 5 hours.

<Preparation Example 6>

Preparation of needle-shaped Spongilla lacustris spicules with pores formed on the 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 3 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.

<Production Example 7>

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 8>

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).

<Production Example 9>

Manufacturing of bio-heavy oil

Waste oil and fat obtained by mixing 62 wt% of animal waste pig, 17 wt% of animal waste, and 21 wt% of sewage oil residue were heated at a temperature of 48° C., liquefied, and filtered to remove solids. The filtered liquefied waste oil was contacted with magnesium and anhydrous sodium sulfate (Na ₂ SO ₄ ) to remove moisture, and then filtered to pre-treat the liquefied waste oil.

After preparing a raw material mixture by mixing the liquefied waste oil and 77% by weight of the ethanol aqueous solution solvent in which the pretreatment is completed in a 1:0.5 weight ratio; Bio-heavy oil was prepared by reacting the raw material mixture at a temperature of 360 °C and a pressure of 180 bar, which is a supercritical state of the alcohol aqueous solution solvent.

<Production Example 10>

Manufacturing of bio-heavy oil

Bio-heavy oil was prepared in the same manner as in Preparation Example 3; Instead of the ethanol aqueous solution solvent, an aqueous alcohol solution solvent in which ethanol and methyl propyl kebinol were mixed in a volume ratio of 1: 0.5 was used.

<Examples and Comparative Examples>

Fine aggregate, coarse aggregate, and function-improving binder mixed with the components and contents as shown in Table 1 below were put in a forced mixing mixer, then mixed under dry mixing conditions for 3 minutes, and components and contents as shown in Table 1 below The function-improving admixture and water mixed with the mixture were simultaneously added and mixed for 2 minutes to prepare a shrinkage-reducing type super-strength and crude-strength cement concrete composition and a comparative concrete composition.

Category (wt%) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 fine aggregate 38 38 38 38 38 coarse aggregate 31 31 31 31 31 water 3 3 3 3 3 Functional improvement binder 19 19 19 19 19 (parts by weight) crude steel portland cement
(Powder: 4,650 ㎠/g) 100 100 100 100 100 Calcium sulfoaluminate 35 35 35 35 35 Potassium Fluoride Nickel Cobalt 11
[Production Example 1] 11
[Production Example 2] 11
[Production Example 2] - - Blast Furnace Slag Fine Powder 8 8 8 8 8 Ladle Slag ⁽¹⁾ 5 5 5 - - tin oxide 4
[Production Example 3]
4
[Production Example 4] 4
[Production Example 5] - 4
[normal
tin oxide powder] Potassium hexafluoromanganate 5 5 5 - - spicule 3
[Production Example 6] 3
[Production Example 7] 3
[Production Example 8] - - 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 Functional admixture 9 9 9 9 9 (parts by weight) Acrylic Latex ⁽²⁾ 100 100 100 100 100 Polymethylmethacrylate-(adamantyl)acrylate copolymer 75 75 75 - 75 Hydroxyfluorine (meth)acrylate ⁽³⁾ 58 58 58 - - 2-thio-4-amino pyrimidine derivatives
[Formula 1-1] 12 12 12 - - bio heavy oil 7
[Production Example 9] 7
[Production Example 9] 7
[Production Example 10] - - Rimocitrine 2 2 2 - - apigenin 2 2 2 - - antifoam 0.8 0.8 0.8 0.8 0.8 air entrainment agent 1.2 1.2 1.2 1.2 1.2

상기 식에서,
R¹은 에틸아민이고,
R²는 피페리디닐 메틸아민이고,
X는 F이다.
⁽¹⁾ Ladle slag: silicon oxide (SiO ₂ ) 18.7 wt%, aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) 10.8 wt%, iron oxide (Fe ₂ O ₃ ) 7.4 wt%, calcium oxide (CaO) 42.5 wt% , magnesium oxide (MgO) 1.4 wt%, sulfur trioxide (SO ₃ ) 2.7 wt%, sodium oxide (Na ₂ O) 0.3 wt%, potassium oxide (K ₂ O) 0.2 wt%, sulfur (S) 1.1 wt%, iron (Fe) 6.5 wt% and phosphorus (P) 0.5 wt% were used.

⁽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⁾ Hydroxyfluorine (meth)acrylate: 3-(perfluorobutyl)-2-hydroxypropyl (meth)acrylate and 3-(perfluorohexyl)-2-hydroxypropyl (meth)acrylate A mixture of 1: 1 by weight is used.

[Formula 1-1]

In the above formula,
R ¹ is ethylamine,
R ² is piperidinyl methylamine,
X is F.

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>

Slump test (degree of kneading) according to the method stipulated in KS F 2402 for the shrinkage-reducing super-strength and crude-strength cement concrete compositions according to Examples 1 to 3 and the cement concrete compositions for comparison according to Comparative Examples 1 and 2 of the present invention was performed. 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 24 24 24 24 24 after 20 minutes 22 22 23 18 20 after 30 minutes 20 21 21 13 17 after 40 minutes 18 19 20 8 12

As can be seen in Table 2, the shrinkage-reducing type super crude steel and crude steel 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 could check

<Test Example 2>

In order to understand the characteristics of the shrinkage-reduced initial steel and crude steel cement concrete composition according to the present invention in more detail, the shrinkage-reduced initial steel and crude steel cement concrete compositions and Comparative Examples 1 and 2 according to Examples 1 to 3 of the present invention The properties of the comparative concrete compositions were evaluated according to the results, 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 0.005 0.002 0.001 0.35 0.11 Compressive strength (MPa)_12 hours KS F 2405 19 21 23 9 13 Compressive strength (MPa)_28 days KS F 2405 32 33 36 20 22 Flexural strength (MPa)_12 hours KS F 2405 5.9 6.3 6.4 2.7 3.1 Flexural strength (MPa)_28 days KS F 2405 9.3 9.4 9.6 5.1 6.2 Adhesive strength (MPa)_12 hours KS F 2762 2.7 2.9 3.2 0.8 1.7 Adhesive strength (MPa)_28 days KS F 2762 3.6 3.7 4.2 1.5 2.1 Salt penetration resistance (coulomb) KS F 2711 794 723 680 1557 1370 Freeze-thaw resistance (%) KS F 2456 88 90 92 65 72 Wear resistance (mm) ASTM C 779 0.07 0.05 0.03 0.25 0.21 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 -0.1 -0.1 -0.9 -0.7 sulfuric acid -0.03 -0.01 -0.01 -0.7 -0.4 sodium hydroxide 0.3 0.2 0.2 1.5 0.7 Anti-rust rate (%) KS F 2561 93 94 96 74 83 Absorption rate (%) KS F 4004 0.5 0.4 0.2 2.9 1.2

As can be seen in Table 3, the shrinkage-reducing type super crude steel and crude steel cement concrete compositions according to Examples 1 to 3 were compared with the comparative cement concrete compositions according to Comparative Examples 1 and 2, and the rate of change in length according to drying shrinkage I was able to confirm this little. In addition, the shrinkage-reduced super-strength and crude-strength cement concrete compositions according to Examples 1 to 3 have 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 a functional improving binder, 0.5 to 20% by weight of a functional improving admixture, and 0.1 to 5% by weight of water;
The function-improving 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 potassium nickel cobalt fluoride, 1 to 20 parts by weight of fine blast furnace slag powder, 0.1 to 10 parts by weight of ladle slag, oxidized 0.1 to 10 parts by weight of tin, 0.1 to 10 parts by weight of potassium hexafluoromanganate, and 0.1 to 10 parts by weight of spicule;
The function-improving admixture is 100 parts by weight of acrylic latex, 70 to 90 parts by weight of polymethyl methacrylate-(adamantyl) acrylate copolymer, 50 to 70 parts by weight of hydroxyfluorine (meth)acrylate, and Formula 1 below. Reduced shrinkage, characterized in that it contains 10 to 30 parts by weight of the indicated 2-thio-4-amino pyrimidine derivative, 0.1 to 10 parts by weight of bio-heavy oil, 0.1 to 10 parts by weight of limocitrin, and 0.1 to 10 parts by weight of apigenin. Type Crude Steel and Crude Steel Cement Concrete Composition.
[Formula 1]

In the above formula,
R ¹ is alkyl having 1 to 6 carbon atoms or (alkyl having 1 to 6 carbon atoms)amine,
R ² is (alkyl having 1 to 6 carbons)amino(alkyl of 1 to 6 carbons)amine or piperidinyl (alkyl of 1 to 6 carbons)amine,
X is F or Cl.
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 with hydrochloric acid solution, 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
Shrink-reduced chozo steel and Crude cement concrete composition.
3. The method of claim 2,
The basic compound is a 3 to 7 N concentration of calcium hydroxide (Ca(OH) ₂ ) and 3 to 7 N concentration of magnesium hydroxide (Mg(OH) ₂ ) 1: 0.1 to 0.5 volume ratio characterized in that the mixture Shrink-reducing ultra-precise steel and crude steel cement concrete composition.
According to claim 1,
The bio heavy oil
Removing the solids by heating at least one type of waste oil selected from the group consisting of animal waste pig, animal waste waste, sewage oil residue, and mixtures thereof at a temperature of 40 to 50 ° C., liquefying it, and then filtering; After removing the moisture by contacting the filtered liquefied waste oil with magnesium and anhydrous sodium sulfate (Na ₂ SO ₄ ), pretreatment by filtration; preparing a raw material mixture by mixing the pre-treated liquefied waste oil and 70 to 95% by weight of an aqueous alcohol solution solvent in a 1:0.1 to 0.5 weight ratio; and reacting the raw material mixture at a temperature of 200 to 600° C. and a pressure of 100 to 250 bar, which is a supercritical state of the alcohol aqueous solvent, to prepare bio-heavy oil; characterized in that it is prepared by a manufacturing method comprising: Shrink-reducing ultra-precise steel and crude steel cement concrete composition.
A road pavement maintenance method using the shrinkage-reducing type steel and crude steel cement concrete composition according to any one of claims 1 to 4,
removing the deteriorated, damaged or contaminated portion of the construction target surface; cleaning the removed area; Primer or blooming treatment on the cleaned area; pouring the shrinkage-reducing super-strength steel and crude-strength cement concrete composition on the primer or blooming-treated upper part; 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 road pavement maintenance method comprising the step of curing.