WO2012067304A1 - Composition composite organique/inorganique à base de silicate-formiate et composition de béton la contenant - Google Patents

Composition composite organique/inorganique à base de silicate-formiate et composition de béton la contenant Download PDF

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Publication number
WO2012067304A1
WO2012067304A1 PCT/KR2010/009259 KR2010009259W WO2012067304A1 WO 2012067304 A1 WO2012067304 A1 WO 2012067304A1 KR 2010009259 W KR2010009259 W KR 2010009259W WO 2012067304 A1 WO2012067304 A1 WO 2012067304A1
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WIPO (PCT)
Prior art keywords
concrete
formate
weight
silicate
inorganic composite
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PCT/KR2010/009259
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English (en)
Korean (ko)
Inventor
김현배
이종인
김우재
길배수
김도수
박용순
강용식
Original Assignee
주식회사 포스코건설
주식회사 트라이포드
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Publication of WO2012067304A1 publication Critical patent/WO2012067304A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/24—Sea water resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/26—Corrosion of reinforcement resistance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to a silicate-formate-based organic-inorganic composite composition and concrete composition using the same, which can be used for coastal concrete structures to be constructed in coastal and coastal landfills, more specifically, to inhibit the shrinkage of concrete structures,
  • the present invention relates to a silicate-formate organic-inorganic composite composition capable of improving the penetration resistance of sulfate ions and the corrosion resistance of reinforcing bars and a concrete composition to which the same is applied.
  • Concrete used in coastal concrete structures has a high risk of cracking due to shrinkage stress due to self-shrinkment and dry shrinkage, and it is exposed to humid environments due to salt and sea salt caused by sea water and chlorine ions and sulfuric acid. Concrete may be corroded by salts and moisture, and reinforcing steel reinforcing inside the concrete may be corroded by neutralization. As a result, the concrete structure is rapidly deteriorated and the service life is significantly reduced, thereby increasing the damage of the structure.
  • the present invention has been made to solve the problems of the prior art as described above, the problem to be solved in the present invention is to suppress the shrinkage of the concrete structure, improve the penetration resistance and reinforcing corrosion resistance of chlorine ions and sulfate ions at the same time It is an object of the present invention to provide a silicate-formate-based organic-inorganic composite composition and a concrete composition to which the same is applied.
  • the present invention is a silicate comprising 30 to 60% by weight of a fluorine-containing silica compound, 5 to 30% by weight of sulfazesin, 5 to 20% by weight of maleic anhydride-acryl copolymer and 30 to 60% by weight of a formate-based compound. It provides a formate organic-inorganic composite composition.
  • the fluorine-containing silica compound is preferably a mixture of H 2 SiF 6 and water.
  • the formate compound is preferably selected from the group consisting of calcium formate and barium formate and mixtures thereof.
  • the present invention provides a concrete composition comprising 0.2 to 3.0 parts by weight of the silicate-formate organic-inorganic composite composition described above with respect to 100 parts by weight of the binder (Binder) used in concrete.
  • the concrete is one kind of ordinary portland cement; One slag cement; Two slag cements; 5 to 39 weight percent fly ash and one kind of ordinary Portland cement by balance; Fly ash 5 to 39% by weight and balance one type of slag cement; It is preferably selected from the group consisting of 5 to 39% by weight of fly ash and the balance of two kinds of slag cement and mixtures thereof.
  • silicate-formate-based organic-inorganic composite composition When applying the silicate-formate-based organic-inorganic composite composition according to the present invention, it is possible to suppress the shrinkage of the coastal concrete structures constructed in the coastal and coastal landfills, improve the penetration resistance and reinforcing corrosion resistance of chlorine ions and sulfate ions It has an effect.
  • 1 is a photograph showing a plate-ring restraint crack test mold.
  • Figure 2 is a graph showing the results of measuring the concrete fluidity according to the Examples and Comparative Examples of the present invention.
  • Figure 3 is a graph showing the results of measuring the concrete compressive strength according to the embodiment and the comparative example of the present invention.
  • Figure 4 is a photograph showing the salt resistance measurement results according to the Examples and Comparative Examples of the present invention.
  • the silicate-formate organic-inorganic composite composition according to the present invention improves the shrinkage resistance of the concrete to suppress the shrinkage crack, and chemically immobilizes chlorine ions and sulfate ions penetrated into the concrete to reduce the concentration of free chlorine ions and sulfate ions You can. Through this, the diffusion coefficient and penetration depth of chlorine ions and sulfate ions in concrete can be reduced, and a protective layer can be formed on the surface of the reinforcing bar to efficiently inhibit the penetration of chlorine ions and sulfate ions. In addition, it is possible to prevent the penetration of the chlorine ions and sulfate ions to improve the corrosion resistance of the reinforcing steel in the concrete.
  • the present invention is a silicate comprising 30 to 60% by weight of a fluorine-containing silica compound, 5 to 30% by weight of sulfazesin, 5 to 20% by weight of maleic anhydride-acryl copolymer and 30 to 60% by weight of a formate-based compound. It provides a formate organic-inorganic composite composition.
  • a dense protective layer of FeF 2 -SiO 2 is formed on the surface of the rebar due to the chemical reaction of silica and glass fluorine on the surface of the reinforcing concrete. .
  • the protective layer essentially blocks the penetration of chlorine ions diffused in the concrete, it can effectively suppress the reinforcement corrosion.
  • silica and free fluoride ions are obtained through hydrolysis of silicic fluoride (SiF 6 2 ⁇ ) dissociated from hydrofluoric acid (H 2 SiF 6 ). Therefore, the fluorinated silica compounds of the present invention is preferably a mixture of water and H 2 SiF 6.
  • the fluorine-containing silica compound is preferably 2 to 50% by weight of silica, 1 to 20% by weight of free fluorine ion (F ⁇ ), and the balance after the hydrolysis reaction.
  • the silica is in the range of 2 to 50% by weight, the glass fluorine ion is preferably limited to the range of 1 to 20% by weight.
  • the fluorine-containing silica compound is used 30 to 60% by weight in the total composition, when the content is less than 30% by weight does not form a sufficient impermeable protective layer, the effect of improving the shrinkage resistance is minimal, the content is 60% by weight If the percentage is exceeded, the improvement effect is insignificant and not only uneconomical, but rather there is a problem in that the physical properties of the concrete are lowered.
  • Sulfazecin is used in the total composition of the present invention 5-30% by weight.
  • the content is less than 5% by weight, the chlorine ion immobilization reaction of sulfazin does not occur sufficiently, and the freezing effect of free chlorine ions is insignificant, and when the content is more than 30% by weight, it is expected to be overused. It is difficult and uneconomical, rather there is a problem that the physical properties of the concrete is lowered.
  • Maleic anhydride-acrylic copolymer is a component involved in the concrete slump releasing effect, and 5 to 20% by weight of the total composition is used.
  • the effect of improving the performance of maintaining concrete fluidity is insignificant, and when the content is more than 20% by weight, the improvement of the effect is low compared to the excess amount, which is uneconomical and the problem of deteriorating concrete properties itself. have.
  • the action of the formate compound is to improve the sulfate resistance of the concrete.
  • formate-based compound examples include calcium formate and barium formate, and they are preferably used alone or in combination. Therefore, the formate compound of the present invention can be used by selecting one or more from the group consisting of calcium formate and barium formate.
  • formate-based compound is by stabilizing the free sulfuric acid ions by chemical adsorption (ion exchange reaction) of the free sulfuric acid ion permeation from the outside of the concrete with water-insoluble compound such as CaSO 4, BaSO 4 It is effective in effectively removing free sulfate ions penetrated into concrete.
  • the formate-based compound is used in the total composition of the present invention.
  • the degree of stabilization of free sulfate ions is insignificant, and when the content exceeds 60% by weight. Compared with the improvement of the effect is insignificant as well as the problem of deteriorating the physical properties of the concrete occurs.
  • the silicate-formate-based organic-inorganic composite composition prepared as described above may be variously applied to cement paste, mortar, concrete, and the like, and the application target thereof is not particularly limited. Considering the aspects in which concrete is mainly used in structures used in the marine environment, it can be most usefully applied to concrete compositions. Specifically, the silicate-formate-based organic-inorganic composite composition can be applied to both construction and civil engineering structures installed on the coast, such as coastal landfill structures, coastal docks, coastal bridges, coastal power plants, coastal tunnels.
  • the content of the silicate-formate-based organic-inorganic composite composition is preferably added 0.2 to 3.0 parts by weight based on 100 parts by weight of the binder (Binder) used in the concrete.
  • the silicate-formate organic-inorganic composite composition is included in less than 0.2 parts by weight, the effect of shrinkage inhibition, penetration resistance of chlorine and sulfate ions and improvement of reinforcing corrosion resistance cannot be sufficiently exhibited.
  • added in excess of 3.0 parts by weight is not only the improvement effect compared to the added amount is not enough, there is a problem that the physical properties of the concrete worsens.
  • the concrete is one kind of ordinary portland cement; One slag cement; Two slag cements; 5-30% by weight of fly ash and the balance of one kind ordinary portland cement; 5 to 30% by weight of fly ash and the balance of one kind of slag cement; And 5 to 30% by weight of fly ash (FA) and the balance are preferably selected from the group consisting of two slag cements and mixtures thereof.
  • one type of slag cement is composed of 5-30% by weight of blast furnace slag (BFS) and the balance is composed of one type of ordinary portland cement, and the second type of slag cement is blast furnace slag (BFS) 30 60% by weight and the balance are composed of one common Portland cement.
  • silicate-formate-based organic-inorganic composite composition as shown in Table 1 below, was used.
  • silicate-formate-based organic-inorganic composite composition composed of the above composition to the concrete formulation of Table 2 used in the coastal civil engineering structures were divided into Comparative Examples and Examples to prepare concrete.
  • the comparative example is a case in which the silicate-formate-based organic-inorganic composite composition is not included in the concrete formulation, and Examples 1 and 2 are respectively 0.5 parts by weight and 1.0 parts by weight, based on 100 parts by weight of the binder used in the concrete. It was supposed to include parts by weight.
  • a concrete a two-component mixed cement composed of 50% by weight of ordinary plain Portland cement and 50% by weight of blast furnace slag powder was used.
  • Performance evaluation of the concrete according to the comparative example and Examples 1 and 2 is characterized by the fluidity (slump flow), compressive strength (age 7 days, 28 days), shrinkage crack resistance, salt resistance and chemical resistance (sulfate resistance) of the concrete Was carried out.
  • Chloride resistance was measured for chlorine ion penetration depth after immersing the concrete specimens cured for 28 days according to the examples in high concentration brine (3% NaCl aqueous solution) for 7 days and 56 days, and the chemical resistance was 5% H 2 SO 4 ) aqueous solution of 10x20cm sized concrete specimens were cured for 28 days, and then evaluated by changing the weight of the specimen by chemical erosion after immersion for 7 days and 28 days.
  • Examples 1 and 2 to which the composition of the present invention is added have a fluidity and compressive strength equal to or higher than those of the comparative example, thereby not affecting the concrete basic properties. It was confirmed that.
  • Shrinkage crack resistance was improved in the crack pattern of the concrete in Example 1 and Example 2 and significantly reduced the crack area as compared to the comparative example as shown in Table 3, and was more remarkable as the addition rate of the composition of the present invention increases.
  • the sulphate resistance of the concrete in the state immersed in a high concentration of sulfuric acid solution showed a high sulphate resistance by reducing the weight loss rate of the concrete by the sulphate in both Examples 1 and 2 compared to the comparative example, the composition of the present invention It was more remarkable as the addition rate of ( Figure 5) increased. This is judged to suppress the weight loss caused by erosion of the concrete by the effect of the formate-based compound contained in the composition of the present invention to stabilize free sulfate ions penetrated into the concrete with insoluble salts.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)

Abstract

La présente invention porte sur une composition composite organique/inorganique à base de silicate-formiate pouvant être utilisée dans une structure de béton côtière construite sur la côte et des terrains récupérés côtiers et sur une composition de béton formée par application de celle-ci et, plus spécifiquement, sur une composition composite organique/inorganique à base de silicate-formiate permettant d'inhiber le retrait d'une structure en béton et d'accroître la résistance à la pénétration d'ions chlorures et d'ions sulfates et la résistance à la corrosion d'une barre de fer et sur une composition de béton formée par application de celle-ci. Si la composition composite organique/inorganique à base de silicate-formiate de la présente invention est appliquée, le retrait d'une structure en béton côtière construite sur la côte et sur des terrains récupérés côtiers peut être supprimé et la résistance à la pénétration d'ions chlorures et d'ions sulfate et la résistance à la corrosion d'une barre de fer peuvent être accrues.
PCT/KR2010/009259 2010-11-18 2010-12-23 Composition composite organique/inorganique à base de silicate-formiate et composition de béton la contenant WO2012067304A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020100114898A KR101083012B1 (ko) 2010-11-18 2010-11-18 실리케이트­포르메이트계 유무기 복합 조성물 및 이를 포함하는 콘크리트 조성물
KR10-2010-0114898 2010-11-18

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WO2012067304A1 true WO2012067304A1 (fr) 2012-05-24

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02221140A (ja) * 1989-02-21 1990-09-04 Nippon Cement Co Ltd モルタルまたはコンクリートの白華防止剤および白華防止方法
EP0562651A1 (fr) * 1992-03-26 1993-09-29 Nobel Paint and Adhesives AB Mortier
US5814253A (en) * 1993-03-25 1998-09-29 Thermoflex, Inc. Process for making a lightweight, cementitious, three dimensional structure
KR100461763B1 (ko) * 2001-10-25 2004-12-14 (주)아텍스 콘크리트 급결제

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02221140A (ja) * 1989-02-21 1990-09-04 Nippon Cement Co Ltd モルタルまたはコンクリートの白華防止剤および白華防止方法
EP0562651A1 (fr) * 1992-03-26 1993-09-29 Nobel Paint and Adhesives AB Mortier
US5814253A (en) * 1993-03-25 1998-09-29 Thermoflex, Inc. Process for making a lightweight, cementitious, three dimensional structure
KR100461763B1 (ko) * 2001-10-25 2004-12-14 (주)아텍스 콘크리트 급결제

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CN102531444A (zh) 2012-07-04
CN102531444B (zh) 2015-04-15
KR101083012B1 (ko) 2011-11-15

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