WO2018124485A1 - Agrégats fins de béton auto-réparant utilisant du laitier réducteur de fourneau à arc électrique type sts, leur procédé de fabrication, et béton auto-réparant les utilisant - Google Patents

Agrégats fins de béton auto-réparant utilisant du laitier réducteur de fourneau à arc électrique type sts, leur procédé de fabrication, et béton auto-réparant les utilisant Download PDF

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WO2018124485A1
WO2018124485A1 PCT/KR2017/013325 KR2017013325W WO2018124485A1 WO 2018124485 A1 WO2018124485 A1 WO 2018124485A1 KR 2017013325 W KR2017013325 W KR 2017013325W WO 2018124485 A1 WO2018124485 A1 WO 2018124485A1
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Prior art keywords
self
sts
healing
healing concrete
weight
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PCT/KR2017/013325
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English (en)
Korean (ko)
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최영철
박병선
오성우
정상화
최성철
이광명
Original Assignee
(재) 한국건설생활환경시험연구원
성균관대학교산학협력단
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Publication of WO2018124485A1 publication Critical patent/WO2018124485A1/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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/02—Agglomerated materials, e.g. artificial aggregates
    • C04B18/021—Agglomerated materials, e.g. artificial aggregates agglomerated by a mineral binder, e.g. cement
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/141—Slags
    • C04B18/142—Steelmaking slags, converter slags
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0016—Granular materials, e.g. microballoons
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0076—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials characterised by the grain distribution
    • C04B20/008—Micro- or nanosized fillers, e.g. micronised fillers with particle size smaller than that of the hydraulic binder
    • 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/06—Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
    • C04B40/0675—Mortars activated by rain, percolating or sucked-up water; Self-healing mortars or concrete
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10—Accelerators; Activators
    • 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 fine aggregate for self-healing concrete using STS (stainless steel slag) furnace slag, a method of manufacturing the same, and a self-healing concrete using the same, and more particularly, to the strength of using STS furnace slag as a cement substitute.
  • STS electric furnace slag is made of fine aggregate for self-healing concrete having spherical particle shape, and the fine aggregate is broken when cracking occurs without affecting strength expression during mixing.
  • the present invention relates to a fine aggregate for self-healing concrete using STS electric furnace reducing slag, which is capable of self-healing of cracks in an air (in air) state by reacting with CO 2 ), a method of manufacturing the same, and self-healing concrete using the same.
  • Representative techniques for imparting self-healing ability to concrete include a technique using various inorganic binders, a technique using microorganisms such as bacteria, and a technique using capsule-polymers [Patent Documents 1 to 3].
  • Patent Documents 1 to 3 For example, considering economical aspects and applicability of concrete structures, self-healing methods using inorganic binders and bacteria are currently the most prominent.
  • Steel slag is composed of iron ore, coke, and limestone as raw materials in blast furnace slag generated from sintering and steel making processes in the blast furnace and converter iron slag generated in the steelmaking process of steel making, and scrap metal such as iron scrap.
  • the electricity generated can be divided into three types of slag.
  • dual furnace slag is divided into oxidation slag and reducing slag as a result of process differentiation in order to improve productivity and molten steel quality in the steelmaking method of the furnace. Since it is in an unstable state due to the incorporation of the expandable material, the expansion and collapse property is high, and as a construction material, stability has not been secured and all of it has been discarded.
  • the reduced slag powder of STS furnace is known to contain a large amount of fine powder of gamma ctus (hereinafter referred to as "gamma-C 2 S"), unlike ⁇ -C 2 S which is generally contained in cement.
  • gamma-C 2 S reacts with water to harden, whereas gamma-C 2 S reacts with CO 2 in air to produce calcite.
  • STS electric furnace slag fine powder which is a kind of electric steelmaking slag, contains a large amount of gamma-C 2 S at about 38% by weight of the total composition. have.
  • gamma-C 2 S in the cement composites, and CO 2 when even hydration progresses gamma-C 2 S within the cement composite material is to remain as unreacted substances and due to cracks generated in the concrete exposed to air Reacts to produce calcite and self-healing cracks.
  • the reduced slag fine powder when used as a cement substitute for STS furnace, the reduced slag for STS furnace remains unreacted in the cement paste because it has no hydraulic and latent hydraulic properties. As it increases, the strength of the concrete decreases.
  • FIG. 2 shows the compressive strength relation according to the reduction slag substitution rate of the STS furnace, and the compressive strength decreases as the reduction slag substitution rate of the STS furnace increases
  • FIG. 3 shows the setting time according to the reduction slag substitution rate of the STS furnace.
  • the present inventors have tried to improve the problems of strength reduction and coagulation delay when using the STS furnace slag as a cement substitute, as a result of producing a fine aggregate having a spherical particle form of the STS furnace slag of the binder when blending
  • the present invention was completed by confirming that the reduced slag aggregate was broken by STS electricity when the crack occurred without affecting the strength expression and reacted with carbon dioxide in the air to self-healing the crack.
  • Patent Document 1 Republic of Korea Patent Publication No. 2015-0055589 (published May 21, 2015)
  • Patent Document 2 Korean Patent No. 1120078 (2012.03.23. Notification)
  • Patent Document 3 3. Republic of Korea Patent Publication No. 2016-0139315 (published Dec. 7, 2016)
  • Non-Patent Document 1 Journal of the Korea Academia-Industrial cooperation Society, 2014, 15, 6890-6897.
  • Another object of the present invention to provide a method for producing the fine aggregate for self-healing concrete.
  • Still another object of the present invention is to provide self-healing concrete using the fine aggregate for self-healing concrete.
  • the present invention is spherical particles in which 15 to 25 parts by weight of a liquid alkali activator is mixed and molded with respect to 100 parts by weight of a mixed powder composed of 80 to 90 wt% of reduced slag fine powder and 10 to 20 wt% of general Portland cement. It provides a fine aggregate for self-healing concrete having a form.
  • the finely reduced slag powder of STS electric furnace has a particle size of 35 ⁇ m or less, and contains gamma-C 2 S as a main component.
  • the present invention is the first step of injecting a mixed powder consisting of 80 to 90% by weight of reduced slag fine powder and 10 to 20% by weight of ordinary portland cement in an STS electric furnace having a particle size of less than 35 ⁇ m in a granulator equipped with a rotating disk, Self-healing concrete comprising a second step of producing a spherical shaped body by rotating a rotating disk in the granulator while spraying 15 to 25 parts by weight of a liquid alkali activator to the granulator and a third process of curing the spherical shaped body It provides a method for producing fine aggregate.
  • the disk provided in the granulator has an inclination of 50 to 65 degrees from the vertical, and the disk is rotated for 20 to 40 rpm and 10 to 20 minutes to form a spherical particle shape.
  • the curing is carried out at 50 to 70 °C and the particle size of the fine aggregate to be distributed to 5mm or less.
  • the fine aggregates for self-healing concrete containing gamma-C 2 S ( ⁇ -2CaO ⁇ SiO 2 ) react with carbon dioxide (CO 2 ) exposed to the crack surface of mortar or concrete.
  • CO 2 carbon dioxide
  • the amount (S / C) of the fine aggregates (S) used for self-healing concrete is used two to three times compared to the cement (C).
  • the present invention by providing a reduced aggregate slag containing a large amount of gamma-C 2 S component as a fine aggregate having a spherical particle form, when the crack occurs in the mortar or concrete and the fine aggregate exposed to the crack and Carbon dioxide (CO 2 ) is reacted to produce a calite (calcite), it is possible to provide a self-healing concrete capable of self-healing of cracks in the air (in air) state without affecting the strength expression during blending.
  • CO 2 Carbon dioxide
  • Figure 2 is a result showing the compressive strength relationship according to the reduction slag substitution rate of STS electric furnace
  • Figure 3 is a result showing the relationship between the setting time of the slag substitution rate of the STS furnace
  • FIG. 7 is a particle size distribution diagram of the reduced slag fine aggregate STS furnace according to the production method of the present invention.
  • FIG. 11 is an SEM image of the self-healing product generated in the crack plane of FIG. 10.
  • FIG. 13 is a measurement result of water flow of self-healing concrete according to a comparative example of the present invention.
  • the present invention with respect to 100 parts by weight of the mixed powder consisting of 80 to 90% by weight of reduced slag fine powder and 10 to 20% by weight of ordinary Portland cement,
  • liquid alkali activator 15 to 25 parts by weight of a liquid alkali activator provides a fine aggregate for self-healing concrete having a spherical particle shape mixed and molded.
  • the STS electric furnace slag fine powder of the present invention contains about 38% by weight of gamma-C 2 S ( ⁇ -2CaO.SiO 2 ) in a total composition, and the present invention provides gamma-C 2.
  • the reduced slag of STS electric furnace containing S into fine aggregate having spherical particle shape, the reduced slag aggregate aggregate is broken by STS electricity and reacts with carbon dioxide in the air when cracking occurs without affecting the strength expression of the binder during mixing. Characterized in that to heal the cracks.
  • Figure 4 shows the particle size percentage (%) of the reduced slag fine powder by STS, as a result of performing XRD analysis and Rietveld method for the reduced slag fine powder of STS or less than 35 ⁇ m, gamma-C 2 Since the S content is as high as 52%, the present invention contains finely reduced slag powder of STS electric furnace having a particle size of 35 ⁇ m or less.
  • the fine aggregate having the spherical particle shape of the reduced slag of STS furnace is formed after mixing 15 to 25 parts by weight of the liquid alkali activator with respect to 100 parts by weight of the mixed powder consisting of finely powdered slag slag and ordinary portland cement.
  • the liquid alkali activator is less than 15 parts by weight, the amount of liquid is too small to form, and if it exceeds 25 parts by weight, it is too diluted to achieve strength as a fine aggregate.
  • the present invention is the first step of injecting a mixed powder consisting of 80 to 90% by weight of reduced slag fine powder and 10 to 20% by weight of ordinary portland cement in an STS electric furnace having a particle size of less than 35 ⁇ m in a granulator equipped with a rotating disk,
  • It provides a method for producing a fine aggregate for self-healing concrete consisting of a third step of curing the spherical shaped body.
  • the first step of the present invention is a step of injecting a mixed powder consisting of 80 to 90% by weight of reduced slag fine powder and 10 to 20% by weight of ordinary Portland cement into a pelletizer equipped with a rotating disk.
  • STS-electrically reduced slag fine powder is mixed with general portland cement by the expression of expression, but in the range of no problem in compatibility, STS-electrically reduced slag fine powder is mixed with 90 wt% and general portland cement 10 wt%. Powder is preferred.
  • the second step of the present invention is a process of manufacturing a spherical shaped body by rotating a rotating disk in the granulator while spraying 15 to 25 parts by weight of a liquid alkali activator to the granulator. Influence of the amount of alkali, the amount of alkali activator in the liquid phase, the inclination angle of the rotating disk, the rotational speed of the disk has a great influence on the physical properties of the final molded product.
  • Figure 5 shows the size and absorption relationship of the fine aggregate according to the rotating disk inclination angle, so that the disk of rotation in the granulator has a slope of 50 to 65 degrees from the vertical It is desirable to install.
  • Figure 6 shows the size and absorption relationship of the fine aggregate according to the rotational speed of the disk, by rotating the disk under the conditions of the disk rotational speed of 20 to 40rpm and 10 to 20 minutes, spherical particle shape Eggplant manufactures shaped bodies.
  • Figure 7 shows the particle size distribution of the reduced slag fine aggregate STS furnace according to the production method of the present invention, the inclined angle of the rotating disk, the rotational speed of the disk so that the size of the particles meet the range of less than 5mm Determine the molding time.
  • the curing step curing the molded article prepared in the above step for about 12 hours under the conditions of 50 to 70 °C to form a fine aggregate distributed in the particle size of 5mm or less.
  • the present invention is a reaction product (calcite, CaCO) by reacting the fine aggregate for self-healing concrete containing gamma-C 2 S ( ⁇ -2CaO ⁇ SiO 2 ) with mortar or carbon dioxide (CO 2 ) exposed to the crack surface of the concrete 3 )) provide self-healing concrete that can self-heap cracks in air (in air).
  • Figure 8 is as showing the generation mechanism of calcite schematically in the self-healing cone Creek of the present invention, (a) CO 2 reaction before gamma-C 2 S ( ⁇ - 2CaO and SiO 2) is a mortar or When cracks occur in concrete, (b) fine aggregates exposed to cracks and CO 2 react to form calcite and self-healing cracks.
  • FIG. 10 shows the flow rate of curing carbon dioxide for the test specimen, and as the CO 2 curing time increases, the amount of water passing through the cracks per unit time decreases considerably, especially, up to 7 days of age. Is the largest and the flow rate through the crack decreases significantly as the amount of fine aggregate containing reducing slag is increased.
  • FIG. 11 is a SEM photograph of a reaction product of white color generated on the crack surface, and is determined to be calsite.
  • the reduced slag fine aggregate was exposed to the crack surface by gamma-C 2 S containing a large amount of the slag and reacted with carbon dioxide in the air to fill the crack by the reaction product (calcite), thereby reducing the flow rate.
  • FIG. 12 is a 28-day compressive strength relationship according to the amount of reduced slag fine aggregate used in the STS electric furnace of the present invention, it is confirmed that the tendency of the compressive strength decreases as the amount of fine aggregate increases, especially S / C sharply decreases at 3.5 Therefore, the preferred amount of STS furnace slag fine aggregate for self-healing concrete by air curing is 2 to 3 times that of cement.
  • the reduced slag aggregate aggregate is broken by the STS electricity when the crack does not affect the strength expression of the binder during mixing, and reacts with carbon dioxide in the air to heal the crack. It can provide a feature.
  • Figure 13 is a result of measuring the water flow (self flow) of self-healing concrete concrete according to the comparative example of the present invention without the fine aggregate for self-healing concrete, cracks per unit time even if the CO 2 curing time increases Since there is no change in crack width due to the amount of water passing through or CO 2 curing, it supports the absence of self-healing effect on cracks.
  • the mixed powder in which 90% by weight of STS reduced slag fine powder and 10% by weight of ordinary Portland cement was mixed was put into a granulator.
  • the rotating disk in the granulator had an inclination of 65 degrees from the vertical and rotated at a speed of 30 rpm.
  • the mixture weight ratio (S / C) between the cement (C) was mixed to 1, 1.5, 2, 2.5, 3 and 3.5 to prepare a test body.
  • the specimens were cured in water for 6 days and then dried in a constant temperature and humidity room.
  • the specimens were split into pieces by UTM, and both ends were fixed with a spacer of a predetermined size to fix the crack width at 150 ⁇ m. To complete.
  • the specimens were cured in water for 6 days and then dried in a constant temperature and humidity room.
  • the specimens were split into pieces by UTM, and both ends were fixed with a spacer of a predetermined size to fix the crack width at 150 ⁇ m. To complete.
  • q is the crack passage flow rate (mL / s).
  • FIG. 11 is a SEM photograph of a newly generated white reaction product on a cracked surface by splitting a specimen exhibiting self-healing performance after the final CO 2 curing. As shown in FIG. 11, it is determined as calcite.
  • the amount of STS furnace reduced slag aggregate for self-healing concrete by air (air) curing may be determined to be two to three times better than that of cement.
  • Figure 13 is a result of measuring the water flow (Water flow) of the test specimens produced in Comparative Examples 2-7, even if the CO 2 curing time increases, the amount of water passing through the crack per unit time was almost unchanged. From the above results, it was confirmed that there was no change in crack width due to CO 2 curing, so that there was no self-healing effect on cracking.
  • the present invention provides a reduced aggregate slag as a fine aggregate having a spherical particle form, which contains a large amount of gamma-C 2 S component, so that the mortar or When cracks occur in concrete, fine aggregates exposed to the cracks react with CO 2 to generate calcite, thereby providing self-healing concrete capable of self-healing of cracks in air (air).
  • the present invention implements the environmentally friendly advantages and economical useful effects of reducing the production cost by recycling the reducing slag to the conventionally discarded STS electricity.

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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Abstract

La présente invention concerne des agrégats fins de béton auto-réparant utilisant du laitier réducteur de fourneau à arc électrique type STS, leur procédé de fabrication, et le béton auto-réparant les utilisant. La présente invention concerne de fins agrégats de béton auto-réparant utilisant le laitier réducteur de fourneau à arc électrique type STS, leur procédé de fabrication, et le béton auto-réparant les utilisant, les fins agrégats permettant, afin d'améliorer des problèmes tels que la réduction de résistance et le délai de prise lorsque du laitier réducteur de fourneau à arc électrique type STS est utilisé comme substitut du ciment, le laitier réducteur de fourneau à arc électrique type STS à fabriquer en agrégats fins de béton auto-réparant présentant des formes de particules sphériques, et ainsi les fins agrégats sont fracturés lorsque des fissures se produisent sans affecter le développement de résistance durant le mélange et réagissant avec le dioxyde de carbone (CO2) dans l'air, permettant de là l'auto-réparation des fissures sous des conditions de air sec (dans l'air).
PCT/KR2017/013325 2017-01-02 2017-11-22 Agrégats fins de béton auto-réparant utilisant du laitier réducteur de fourneau à arc électrique type sts, leur procédé de fabrication, et béton auto-réparant les utilisant WO2018124485A1 (fr)

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KR1020170000100A KR101863964B1 (ko) 2017-01-02 2017-01-02 Ｓｔｓ 전기로 환원슬래그를 이용한 자기치유 콘크리트용 잔골재, 그의 제조방법 및 그를 이용한 자기치유 콘크리트
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CN115872648B (zh) * 2022-12-05 2024-03-19 深圳大学 自控触发型自修复骨料及其制备方法、滨海自修复混凝土

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