KR102257590B1 - Surface modified blast furnace slag, method for preparing therof, and back fill grout composition using the same - Google Patents
Surface modified blast furnace slag, method for preparing therof, and back fill grout composition using the same Download PDFInfo
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- 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
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- 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
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- 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
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- C04B20/023—Chemical treatment
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- 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
- C04B20/02—Treatment
- C04B20/026—Comminuting, e.g. by grinding or breaking; Defibrillating fibres other than asbestos
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- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
- C04B22/062—Oxides, Hydroxides of the alkali or alkaline-earth metals
- C04B22/064—Oxides, Hydroxides of the alkali or alkaline-earth metals of the alkaline-earth metals
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- 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
- C04B28/14—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 calcium sulfate cements
- C04B28/142—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/144—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being a flue gas desulfurization product
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
- C09K17/42—Inorganic compounds mixed with organic active ingredients, e.g. accelerators
- C09K17/44—Inorganic compounds mixed with organic active ingredients, e.g. accelerators the inorganic compound being cement
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00732—Uses not provided for elsewhere in C04B2111/00 for soil stabilisation
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/70—Grouts, e.g. injection mixtures for cables for prestressed concrete
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- 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
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- 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
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Abstract
본 발명은 아민 화합물과 글리콜 화합물로 이루어진 분쇄조제로 고로슬래그를 표면 개질시킨 6,000g/㎤ 이상 8,000g/㎤ 미만의 분말도를 가지는 표면개질된 고로 슬래그, 이의 제조방법, 및 상기 분말도 6,000g/㎤ 이상 8,000g/㎤ 미만의 표면개질된 고로 슬래그 40 ~ 50중량%, 분말도 2,800~3,800g/㎤인 탈황석고 40 ~ 50중량%, 분말도 3,200~4,000g/㎤ 고칼슘 플라이애시 3 ~ 5중량%, 산화칼슘 1~3 중량%, 및 수산화칼슘 2 ~ 5중량%로 포함하는 배면 충진용 그라우트 조성물에 관한 것으로서, 본 발명에서는 상기 표면개질된 고로슬래그를 사용함으로써 그라우트재의 초기 강도를 확보할 수 있을 뿐만 아니라, 저알칼리성의 배면 충진용 그라우트 조성물을 제공할 수 있게 되다.The present invention is a surface-modified blast furnace slag having a powderiness of 6,000 g/cm 3 or more and less than 8,000 g/cm 3 with a grinding aid consisting of an amine compound and a glycol compound, and a method for producing the same, and the powder 6,000 g 40-50% by weight of surface-modified blast furnace slag of more than /cm3 and less than 8,000g/cm3, 40-50% by weight of desulfurized gypsum with a powderiness of 2,800-3,800g/cm3, and 3,200-4,000g/cm3 of high calcium fly ash It relates to a rear filling grout composition comprising 5% by weight, 1 to 3% by weight of calcium oxide, and 2 to 5% by weight of calcium hydroxide.In the present invention, the initial strength of the grout material is secured by using the surface-modified blast furnace slag. In addition, it is possible to provide a grout composition for filling the back surface of low alkalinity.
Description
본 발명은 표면 개질된 고로슬래그, 이의 제조방법, 및 이를 이용한 배면 그라우트 조성물에 관한 것으로서, 상세하게는 표면 개질시켜 높은 분말도값을 만족하는 고로슬래그와 이의 제조방법, 및 이를 이용하여 초기 강도 등 물성이 우수한 배면 그라우트 조성물에 관한 것이다.The present invention relates to a surface-modified blast furnace slag, a method for producing the same, and a rear grout composition using the same, and in detail, a blast furnace slag that satisfies a high powderiness value by surface modification and a method for producing the same, and initial strength using the same It relates to a back grout composition excellent in physical properties.
일반적으로 토목구조물에서 터파기 등의 작업 과정에서 터파기 면의 안정화를 위하여 차수벽을 설치하게 된다. 차수벽 배면은 지하수나 토양 유실의 위험성을 가지고 있어 차수벽을 설치 후 배면의 공동부가 있을 경우에는 차수성을 갖는 그라우트재를 배면에 투입하여 공동부를 충진하는 공사가 이루어지게 된다. In general, in the process of digging, etc. in a civil engineering structure, an order wall is installed to stabilize the digging surface. Since the rear surface of the order wall has a risk of loss of groundwater or soil, if there is a cavity on the rear surface after installing the order wall, a work is performed to fill the cavity by inserting a water-resistant grout material into the rear surface.
이때 사용되는 기존 배면충진용 그라우트는 대부분 고알칼리성인 포틀랜드 시멘트를 사용하고 있어 지하수 오염원이 되는 문제점이 있다. The existing backfill grout used at this time uses Portland cement, which is mostly highly alkaline, so there is a problem that it becomes a source of groundwater pollution.
또한, 저알칼리 타입의 고로슬래그 기반의 그라우트재가 있으나 고로슬래그의 잠재수경성으로 인해 초기 강도가 낮은 문제점으로 인해 요구성능을 확보하는데 어려움이 있다. In addition, although there is a low alkali type blast furnace slag-based grout material, it is difficult to secure the required performance due to the problem of low initial strength due to the latent hydraulicity of the blast furnace slag.
특허문헌 1에서는 입자가 미세하고 유동성이 뛰어나 주입이 용이하며, 장거리 이송 시에도 재료분리가 발생되지 않고, 양생과정에서도 블리딩이 거의 발생하지 않으며, 기존에 사용하던 이입재에 비해 방수성 및 압축강도가 향상되어 터널 유지관리에 용이하고, 지반침강을 효과적으로 방지할 수 있으므로 터널 배면 공동 뒤채움 이입재로 유용하게 사용할 수 있는, 배면 충진 그라우트용 조성물로서 시멘트 35 ~ 42 중량%, 석회석 45 ~ 55 중량%, 칼슘 설퍼 알루미네이트 3.0 ~ 6.0 중량%, 벤토나이트 1.5 ~ 3.0 중량%, 무수석고 4.0 ~ 6.0 중량%, 폴리카르복실레이트 0.1 ~ 3.0 중량%, 징크 스테아레이트 1.0 ~ 3.0 중량%, 필름형성 아크릴계 파우더 0.3 ~ 1.0 중량% 및 혼화제 0.1 ~ 1.0 중량%로 이루어지는 것을 제시하고 있다.In Patent Document 1, the particles are fine and have excellent fluidity, so injection is easy, material separation does not occur even during long-distance transport, bleeding hardly occurs even in the curing process, and waterproofness and compressive strength are higher than those of existing transfer materials. As it is improved, it is easy to maintain the tunnel and can effectively prevent ground sedimentation, so it can be usefully used as a backfilling material on the back of the tunnel, as a composition for back-filling grout, cement 35 to 42% by weight, limestone 45 to 55% by weight , Calcium Sulfur Aluminate 3.0 to 6.0 wt%, Bentonite 1.5 to 3.0 wt%, Anhydrous Gypsum 4.0 to 6.0 wt%, Polycarboxylate 0.1 to 3.0 wt%, Zinc Stearate 1.0 to 3.0 wt%, Film Forming Acrylic Powder 0.3 It is proposed to consist of ~ 1.0% by weight and 0.1 ~ 1.0% by weight of admixture.
또한, 특허문헌 2에서는 무기계를 사용하여 난연성이 우수한 흡수 겔화성 및 난연성 아크릴레이트계 배면주입 차수제로서, 물, 아크릴아마이드(Acrylamide), 붕산(Boric Acid), 메틸렌비스아크릴아마이드(N, N'-methylenebisacrylamide), 아크릴산(Acryl acid), 암모늄퍼설페이트(Ammonium persulfate), 하이드록시에틸메타아크릴레이트(Hydroxyethyl methacrylate)를 균질 혼합 반응시켜 생성된 A액;과 물, 폴리비닐알코올(Polyvinyl alcohol), 아크릴산(Acryl acid), 수산화마그네슘(Magnesium hydroxide), 소듐퍼설페이트(Sodium persulfate) 및 리튬실리케이트(Lithium silicate)를 균질 혼합 반응시켜 생성된 B액;과 물, 트리에탄올아민(tanol amine)을 균질하게 혼합한 C액;을 포함하여 구성되어, 상기 A액에 상기 C액을 첨가하여 균질 혼합한 후, B액을 혼합하여 주입하는 것을 특징으로 하는 흡수 겔화성 및 난연성 아크릴레이트계 배면주입 차수제를 제시하고 있다.In addition, in Patent Document 2, water, acrylamide, boric acid, methylenebisacrylamide (N, N' -Methylenebisacrylamide), acrylic acid (Acryl acid), ammonium persulfate (Ammonium persulfate), hydroxyethyl methacrylate (Hydroxyethyl methacrylate) A solution produced by homogeneous mixing reaction; and water, polyvinyl alcohol (Polyvinyl alcohol), acrylic acid (Acryl acid), magnesium hydroxide (Magnesium hydroxide), sodium persulfate (Sodium persulfate) and lithium silicate (Lithium silicate) B solution produced by homogeneous mixing reaction; and water, triethanolamine (tanol amine) is homogeneously mixed Consisting of including; Liquid C; after homogeneous mixing by adding the liquid C to the liquid A, and then mixing and injecting the liquid B, an absorption gelling and flame-retardant acrylate-based back injection water-repellent agent is presented, and have.
이에 본 발명에서는 종래 배면충진용 그라우트재가 가지는 초기 강도가 저하되는 문제를 해결할 수 있도록 높은 분말도값을 가지도록 특정 분쇄조제로 표면개질시킨 고로슬래그를 제공하는 데 그 목적이 있다.Accordingly, an object of the present invention is to provide a blast furnace slag surface-modified with a specific grinding aid to have a high powderiness value so as to solve the problem of lowering the initial strength of the conventional grout material for backfilling.
또한, 본 발명의 다른 목적은 높은 분말도값을 가지도록 특정 분쇄조제로 표면개질시킨 고로슬래그의 제조방법을 제공하는 데도 있다.In addition, another object of the present invention is to provide a method for producing blast furnace slag surface-modified with a specific grinding aid so as to have a high powderiness value.
추가로 본 발명은 상기 높은 분말도값을 가지는 표면개질된 고로슬래그를 포함하여 종래 배면충진용 그라우트재가 가지는 여러 가지 문제들을 해결할 수 있는 배면충진용 그라우트재 조성물을 제공하는 데도 그 목적이 있다.In addition, an object of the present invention is to provide a grout material composition for backfilling that can solve various problems of the conventional backfilling grout material, including the surface-modified blast furnace slag having a high powderiness value.
상기 목적을 달성하기 위한 본 발명의 표면개질된 고로 슬래그는 아민 화합물과 글리콜 화합물로 이루어진 분쇄조제로 고로슬래그를 표면 개질시킨 6,000g/㎤ 이상 8,000g/㎤ 미만의 분말도를 가지는 것을 그 특징으로 한다.The surface-modified blast furnace slag of the present invention for achieving the above object is characterized in that it has a powderiness of 6,000 g/cm 3 or more and less than 8,000 g/cm 3 by surface-modified blast furnace slag with a grinding aid consisting of an amine compound and a glycol compound. do.
본 발명의 일 실시예에 따르면, 상기 분쇄조제는 아민 화합물:글리콜 화합물이 30~70:70~30의 중량비로 혼합된 것일 수 있다. According to an embodiment of the present invention, the grinding aid may be a mixture of an amine compound: a glycol compound in a weight ratio of 30 to 70: 70 to 30.
본 발명의 일 실시예에 따르면, 상기 아민 화합물은 디에탄올아민(Diethanolamine), 트리에탄올아민(Triethanol amine), 및 트리이소프로판올 아민(Triisopropanol Amine)으로 이루어진 그룹으로부터 선택되는 1종 이상이며, 상기 글리콜 화합물은 디에틸렌글리콜(DIETHYLENE GLYCOL), 모노에틸렌글리콜(MONO-ETHYLENE GLYCOL), 및 프로필렌글리콜(Propylene Glycol)로 이루어진 그룹으로부터 선택되는 1종 이상인 것이 바람직하다. According to an embodiment of the present invention, the amine compound is at least one selected from the group consisting of diethanolamine, triethanol amine, and triisopropanol amine, and the glycol compound is Diethylene glycol (DIETHYLENE GLYCOL), monoethylene glycol (MONO-ETHYLENE GLYCOL), and propylene glycol (Propylene Glycol) is preferably at least one selected from the group consisting of.
또한, 상기 아민 화합물과 글리콜 화합물로 이루어진 분쇄조제는 상기 고로슬래그 중량에 대하여 0.1~0.5중량%로 혼합되는 것일 수 있다.In addition, the grinding aid made of the amine compound and the glycol compound may be mixed in an amount of 0.1 to 0.5% by weight based on the weight of the blast furnace slag.
또한, 본 발명의 다른 목적을 달성하기 위한 표면개질된 고로 슬래그의 제조방법은 아민 화합물과 글리콜 화합물로 이루어진 분쇄조제와 물을 30:70~50:50의 중량비로 혼합시키는 단계, 및 상기 분쇄조제와 물의 혼합물을 고로슬래그에 첨가하여 3시간 ~ 4시간 동안 분쇄시켜 고로슬래그의 표면을 개질시키는 단계를 포함하는 것을 그 특징으로 한다.In addition, the manufacturing method of the surface-modified blast furnace slag for achieving another object of the present invention is a step of mixing a grinding aid consisting of an amine compound and a glycol compound and water in a weight ratio of 30:70 to 50:50, and the grinding aid It characterized in that it comprises the step of modifying the surface of the blast furnace slag by adding a mixture of and water to the blast furnace slag and pulverized for 3 to 4 hours.
또한, 본 발명은 추가적으로 분말도 6,000g/㎤ 이상 8,000g/㎤ 미만의 표면개질된 고로 슬래그 40 ~ 50중량%, 분말도 2,800 ~ 3,800g/㎤인 탈황석고 40 ~ 50중량%, 분말도 3,200~4,000g/㎤ 고칼슘 플라이애시 3 ~ 5중량%, 산화칼슘 1~3 중량%, 및 수산화칼슘 2 ~ 5중량%로 포함하는 배면 충진용 그라우트 조성물을 제공하는 데도 그 특징이 있다. In addition, the present invention additionally powders 6,000g/cm3 or more and less than 8,000g/cm3 surface-modified blast furnace slag 40-50% by weight, powdery 2,800-3,800g/cm3 of desulfurized gypsum 40-50% by weight, powder degree 3,200 There is also a feature of providing a grout composition for filling the back surface comprising 3 to 5% by weight of high calcium fly ash, 1 to 3% by weight of calcium oxide, and 2 to 5% by weight of calcium hydroxide.
상기 배면 충진용 그라우트 조성물은 pH 11 이하의 저알칼리성인 것이 바람직하다.It is preferable that the grout composition for filling the back surface has a pH of 11 or less and has a low alkalinity.
본 발명에 따르면, 고로슬래그의 반응성을 향상시키기 위하여 아민 화합물과 글리콜 화합물로 이루어진 분쇄조제를 이용하여 일정한 분말도값을 가지는 표면개질된 고로슬래그를 제조하였다.According to the present invention, in order to improve the reactivity of the blast furnace slag, a surface-modified blast furnace slag having a certain powderiness value was prepared by using a grinding aid composed of an amine compound and a glycol compound.
또한, 본 발명에서는 상기 표면개질된 고로슬래그를 사용함으로써 그라우트재의 초기 강도를 확보할 수 있을 뿐만 아니라, 저알칼리성의 배면 충진용 그라우트 조성물을 제공할 수 있게 되었다. In addition, in the present invention, by using the surface-modified blast furnace slag, not only can the initial strength of the grout material be secured, but also a grout composition for filling the back surface of low alkalinity can be provided.
본 발명에서는 고알칼리성인 포틀랜드 시멘트를 사용하지 않기 때문에 지하수 오염 문제를 해결하여 친환경적인 배면충진용 그라우트재를 제공하는 효과를 가진다.In the present invention, since Portland cement, which is highly alkaline, is not used, it has the effect of providing an eco-friendly grout material for backfilling by solving the problem of groundwater contamination.
이하에서 본 발명을 더욱 상세하게 설명하면 다음과 같다. Hereinafter, the present invention will be described in more detail.
본 명세서에서 사용된 용어는 특정 실시예를 설명하기 위하여 사용되며, 본 발명을 제한하기 위한 것이 아니다. 본 명세서에서 사용된 바와 같이, 단수 형태는 문맥상 다른 경우를 분명히 지적하는 것이 아니라면, 복수의 형태를 포함할 수 있다. 또한, 본 명세서에서 사용되는 경우 "포함한다(comprise)" 및/또는 "포함하는(comprising)"은 언급한 형상들, 숫자, 단계, 동작, 부재, 요소 및/또는 이들 그룹의 존재를 특정하는 것이며, 하나 이상의 다른 형상, 숫자, 동작, 부재, 요소 및/또는 그룹들의 존재 또는 부가를 배제하는 것이 아니다.The terms used in this specification are used to describe specific embodiments, and are not intended to limit the present invention. As used herein, the singular form may include the plural form unless the context clearly indicates another case. Also, as used herein, “comprise” and/or “comprising” specify the presence of the mentioned shapes, numbers, steps, actions, members, elements and/or groups thereof. And does not exclude the presence or addition of one or more other shapes, numbers, actions, members, elements and/or groups.
본 발명은 표면개질된 고로슬래그와 이의 제조방법, 및 이를 이용한 배면 충진용 그라우트 조성물에 관한 것이다.The present invention relates to a surface-modified blast furnace slag, a method for manufacturing the same, and a grout composition for filling the back surface using the same.
본 발명에서는 종래 고로슬래그를 포함하는 배면 충진용 그라우트 조성물에서, 고로 슬래그의 잠재수경성으로 인해 초기 강도가 낮은 문제점으로 인해 요구성능을 확보하는데 어려움이 있었고, 이에 따라 상기 고로슬래그의 반응성을 향상시켜 그라우트재의 초기 물성을 향상시킬 수 있는 저알칼리성의 배면충진용 그라우트재를 제공할 수 있다. In the present invention, in the conventional grout composition for filling the back surface containing blast furnace slag, it was difficult to secure the required performance due to the problem of low initial strength due to the latent hydraulicity of the blast furnace slag, and accordingly, the reactivity of the blast furnace slag was improved to grout. It is possible to provide a grout material for backfilling of low alkalinity that can improve the initial properties of ash.
따라서, 상기 고로슬래그의 반응성을 향상하기 위한 방안으로 C3A의 반응성을 향상시킬 수 있는 아민 화합물과 글리콜 화합물로 이루어진 분쇄조제를 이용하여 표면개질시켜 높은 분말도값을 가지는 고로슬래그를 사용한 데 그 특징이 있다.Therefore, as a method for improving the reactivity of the blast furnace slag, a blast furnace slag having a high powderiness value was used by surface modification using a grinding aid consisting of an amine compound and a glycol compound capable of improving the reactivity of C3A. have.
본 발명에 따른 상기 분쇄조제는 아민 화합물:글리콜 화합물을 30~70:70~30의 중량비로 혼합시키는 것이 바람직하며, 상기 아민 화합물이 30 중량부 미만인 경우에는 강도 성능을 향상하는데 어려움이 있으며, 70 중량부를 초과하는 경우에는 가격이 상승하여 경제성의 저하되는 문제가 있어 바람직하지 못하다. The grinding aid according to the present invention is preferably mixed with an amine compound: a glycol compound in a weight ratio of 30 to 70: 70 to 30, and when the amine compound is less than 30 parts by weight, it is difficult to improve strength performance, and 70 If it exceeds parts by weight, it is not preferable because there is a problem that the price increases and the economy is deteriorated.
본 발명에 따른 상기 아민 화합물은 디에탄올아민(Diethanolamine), 트리에탄올아민(Triethanol amine), 및 트리이소프로판올 아민(Triisopropanol Amine)으로 이루어진 그룹으로부터 선택되는 1종 이상이며, 상기 글리콜 화합물은 디에틸렌글리콜(DIETHYLENE GLYCOL), 모노에틸렌글리콜(MONO-ETHYLENE GLYCOL), 및 프로필렌글리콜(Propylene Glycol)로 이루어진 그룹으로부터 선택되는 1종 이상인 것이 바람직하게 사용될 수 있다. The amine compound according to the present invention is at least one selected from the group consisting of diethanolamine, triethanol amine, and triisopropanol amine, and the glycol compound is diethylene glycol (DIETHYLENE GLYCOL), monoethylene glycol (MONO-ETHYLENE GLYCOL), and propylene glycol (Propylene Glycol) can be preferably used one or more selected from the group consisting of.
또한, 상기 아민 화합물과 글리콜 화합물로 이루어진 분쇄조제는 상기 고로슬래그 중량에 대하여 0.1 ~ 0.5 중량%로 혼합되는 것이 바람직하며, 분쇄조제의 함량이 0.1중량% 미만인 경우 그 효과가 미흡하고 0.5중량%를 초과하여 포함될 경우 고로슬래그 입자의 정전기를 확산시켜 분쇄성능을 향상하는 분쇄조제의 분쇄 성능이 더 이상 향상되지 않으며, 경제성이 저하되는 문제가 있어 바람직하지 못하다.In addition, the grinding aid consisting of the amine compound and the glycol compound is preferably mixed in an amount of 0.1 to 0.5% by weight based on the weight of the blast furnace slag, and when the content of the grinding aid is less than 0.1% by weight, the effect is insufficient and 0.5% by weight is If included in excess, the pulverization performance of the pulverizing aid, which improves pulverization performance by spreading static electricity of the blast furnace slag particles, is no longer improved, and there is a problem that economic efficiency is lowered, which is not preferable.
본 발명에 따른 표면개질된 고로슬래그는 그 분말도가 6,000g/㎤ 이상 8,000g/㎤ 미만의 값을 만족하는 것이 바람직하다. It is preferable that the surface-modified blast furnace slag according to the present invention satisfies a value of 6,000 g/cm 3 or more and less than 8,000 g/cm 3.
이는 고로슬래그의 분말도가 6,000g/㎤ 부터는 잠재수경성이 아닌 물과 직접 반응할 수 있는 수경성으로 변화되는 특성이 있기 때문에 그 분말도가 6,000g/㎤ 이상인 것이 바람직하나, 분말도가 8,000g/㎤ 이상인 경우 시멘트와 유사한 성능을 나타내는 것으로 알려져 있으나 분쇄시간의 과량 증가로 인해 경제성 및 공정확보가 어려운 문제점이 있어 바람직하지 못하기 때문이다. This is because the powderiness of blast furnace slag changes from 6,000g/cm3 to hydraulicity that can react directly with water rather than latent hydraulicity, so it is preferable that the powderiness is 6,000g/cm3 or more, but the powderiness is 8,000g/cm3. If it is more than 3 cm3, it is known to exhibit similar performance to cement, but it is not preferable because there is a problem that it is difficult to secure economic efficiency and process due to an excessive increase in pulverization time.
이러한 본 발명에 따른 표면개질된 고로 슬래그는 아민 화합물과 글리콜 화합물로 이루어진 분쇄조제와 물을 30:70~ 50:50의 중량비로 혼합시키는 단계, 및 상기 분쇄조제와 물의 혼합물을 고로슬래그에 첨가하여 3~4 시간 동안 분쇄시켜 고로슬래그의 표면을 개질시키는 단계를 거쳐 제조될 수 있다.The surface-modified blast furnace slag according to the present invention comprises a step of mixing a grinding aid consisting of an amine compound and a glycol compound and water in a weight ratio of 30:70 to 50:50, and adding a mixture of the grinding aid and water to the blast furnace slag It can be prepared through the step of pulverizing for 3 to 4 hours to modify the surface of the blast furnace slag.
즉, 본 발명에 따른 분쇄조제로 표면개질된 고로슬래그는 아민 화합물과 글리콜 화합물로 이루어진 분쇄조제를 이용하여 고로슬래그를 미세하게 분쇄시켜 그 분말도를 원하는 수준으로 향상시킨 것을 의미하며, 상기 높은 분말도를 가지는 고로슬래그는 높은 반응성을 가짐으로써 초기 강도가 우수하고, 저알칼리성을 가지도록 한 데 특징이 있다.That is, the blast furnace slag surface-modified with the pulverizing aid according to the present invention means that the blast furnace slag is finely pulverized using a pulverizing aid composed of an amine compound and a glycol compound to improve its powderiness to a desired level, and the high powder The blast furnace slag having a degree is characterized by having high reactivity, so that it has excellent initial strength and low alkalinity.
이러한 본 발명에 따른 배면 충진용 그라우트 조성물은 상기 분말도 6,000g/㎤ 이상 8,000g/㎤ 미만의 표면개질된 고로 슬래그 40~50중량%, 분말도 2,800 ~ 3,800g/㎤인 탈황석고 40~50중량%, 분말도 3,200~4,000g/㎤ 고칼슘 플라이애시 3 ~ 5중량%, 산화칼슘 1~3 중량%, 및 수산화칼슘 2 ~ 5중량%로 포함하여 이루어진다.The grout composition for filling the back surface according to the present invention includes 40-50% by weight of surface-modified blast furnace slag having a powderiness of 6,000g/cm3 or more and less than 8,000g/cm3, and a desulfurization gypsum having a powderiness of 2,800-3,800g/cm3. % By weight, 3,200 to 4,000 g/cm 3 powder of high calcium fly ash, 3 to 5% by weight, 1 to 3% by weight of calcium oxide, and 2 to 5% by weight of calcium hydroxide.
상기 분말도 6,000g/㎤ 이상 8,000g/㎤ 미만의 표면개질된 고로슬래그는 전체 조성물 중 40 ~ 50중량%로 포함되며, 50중량%를 초과하는 경우 분쇄 공정물의 증가로 경제성의 문제가 있으며, 40중량% 미만일 경우 강도 성능이 낮아지는 문제가 있어 바람직하지 못하다.The surface-modified blast furnace slag of 6,000 g/cm 3 or more and less than 8,000 g/cm 3 of the powder is included in 40 to 50% by weight of the total composition, and when it exceeds 50% by weight, there is a problem of economical efficiency due to an increase in the pulverization process, If it is less than 40% by weight, there is a problem that the strength performance is lowered, which is not preferable.
또한, 상기 탈황석고는 분말도 2,800 ~ 3,800g/㎤인 것으로 전체 조성물 중 40 ~ 50중량%로 포함되며, 40중량% 미만일 경우 자극제의 효과가 낮아져 강도가 낮아지는 문제가 있으며, 50중량%를 초과할 경우 유동성이 감소되는 문제점이 있다. 또한, 그 분말도는 2,800~3,800g/㎤인 것이 분말상의 자극제를 고르게 확산시켜 반응성을 안정적으로 확보하는 면에서 바람직하다. In addition, the desulfurized gypsum has a powder of 2,800 to 3,800 g/cm 3 and is included in 40 to 50% by weight of the total composition, and if it is less than 40% by weight, there is a problem that the strength of the stimulant is lowered and the strength is lowered. If it is exceeded, there is a problem that liquidity decreases. In addition, the powderiness is preferably 2,800 to 3,800 g/cm 3 from the viewpoint of uniformly diffusing the powdery stimulating agent and stably securing the reactivity.
또한, 상기 고칼슘 플라이애시는 분말도 3,200~4,000g/㎤ 인 것으로, 전체 조성물 중 3 ~ 5중량%로 포함되며, 그 함량이 3중량% 미만시 팽창률이 낮아져 공극 충진이 원활하지 않으며, 5중량% 초과시 유동성이 급격하게 감소하여 공극 충진성이 저하되는 문제점이 발생한다. 또한, 그 분말도는 3,200~4,000g/㎤인 것이 분말상의 자극제를 고르게 확산시켜 반응성을 안정적으로 확보하는 면에서 바람직하다. In addition, the high-calcium fly ash has a powder of 3,200 to 4,000 g/cm 3 and is included in 3 to 5% by weight of the total composition, and when the content is less than 3% by weight, the expansion rate is lowered, so that the void filling is not smooth, and 5% by weight. When the% is exceeded, the fluidity rapidly decreases, resulting in a problem that the void fillability is deteriorated. In addition, it is preferable that the powderiness is 3,200 to 4,000 g/cm 3 in terms of stably securing reactivity by spreading the powdery stimulant evenly.
본 발명에 따른 배면 충진용 그라우트 조성물에 포함되는 상기 산화칼슘은 전체 조성물 중 1~3 중량%로 포함되는 것이 바람직하며, 1중량% 미만에서는 그 효과가 미흡하고 3중량%를 초과하는 경우 pH가 급격하게 증가하고 물과의 반응성이 급격하게 상승하여 유동성이 급격하게 감소하는 문제점이 있다. The calcium oxide contained in the grout composition for backfilling according to the present invention is preferably included in 1 to 3% by weight of the total composition, and if it is less than 1% by weight, the effect is insufficient, and when it exceeds 3% by weight, the pH is There is a problem in that the fluidity rapidly decreases due to the rapid increase and the rapid increase in reactivity with water.
또한, 상기 조성물에 포함되는 수산화칼슘은 전체 조성물 중 2 ~ 5중량%로 포함되며, 그 함량이 2중량% 미만시 장기강도가 감소하는 특성이 있으며, 5중량% 초과시 pH가 급격하게 증가하는 문제점이 있다. In addition, calcium hydroxide contained in the composition is contained in 2 to 5% by weight of the total composition, and when the content is less than 2% by weight, long-term strength decreases, and when it exceeds 5% by weight, the pH increases rapidly. have.
본 발명에 따른 배면 충진용 그라우트 조성물은 상기 각 조성을 혼합하여 제조될 수 있으며, 여기에 물을 40중량% 정도 첨가하여 최종 조성물을 제조한다. The grout composition for filling the rear surface according to the present invention may be prepared by mixing each of the above compositions, and about 40% by weight of water is added thereto to prepare a final composition.
이렇게 제조된 본 발명에 따른 배면 충진용 그라우트 조성물은 pH 11 이하의 저알칼리성을 가지는 데 특징이 있다. The grout composition for filling the rear surface according to the present invention thus prepared is characterized in that it has a low alkalinity of pH 11 or less.
이하에서 본 발명의 바람직한 실시예를 상세히 설명하기로 한다. 이하의 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되어서는 안 된다. 또한, 이하의 실시예에서는 특정 화합물을 이용하여 예시하였으나, 이들의 균등물을 사용한 경우에 있어서도 동등 유사한 정도의 효과를 발휘할 수 있음은 당업자에게 자명하다.Hereinafter, a preferred embodiment of the present invention will be described in detail. The following examples are for illustrative purposes only, and the scope of the present invention should not be construed as being limited by these examples. In addition, in the following examples, specific compounds are used for exemplification, but it is obvious to those skilled in the art that even when an equivalent thereof is used, an effect of an equivalent or similar degree can be exhibited.
실시예 : 표면개질된 고로슬래그 제조Example: Preparation of surface-modified blast furnace slag
다음 표 1에 따른 조성으로 구성된 각 분쇄조제와 물을 1:1(50:50)의 중량비로 혼합시키고, 상기 혼합물을 고로슬래그 중량 대비 0.5% 혼합한 뒤 4시간가량 분쇄시켜 표면개질된 고로슬래그를 제조하였다. The blast furnace slag surface-modified by mixing each grinding aid composed of the composition according to Table 1 and water at a weight ratio of 1:1 (50:50), mixing the mixture by 0.5% based on the weight of the blast furnace slag, and pulverizing for about 4 hours. Was prepared.
실험예 1 : 표면개질된 고로슬래그의 분말도와 활성도지수 측정Experimental Example 1: Measurement of powderiness and activity index of surface-modified blast furnace slag
상기 제조된 표면개질된 고로슬래그의 분말도와 활성도지수는 각각 시멘트의 분말도 시험방법(KS L 5106)과 KS F 2563에 따라 측정하였으며, 그 결과를 다음 표 1에 나타내었다. The powderiness and activity index of the prepared surface-modified blast furnace slag were measured according to the powderiness test method of cement (KS L 5106) and KS F 2563, respectively, and the results are shown in Table 1 below.
상기 표면개질된 고로슬래그의 활성도지수는 시멘트 50중량부, 분말도 4,000g/㎤~4,800g/㎤인 고로슬래그 50중량부, 잔골재 245중량부, 물 48.5중량부의 표준배합에 대하여 카르복실계 활성화제의 배합비에 따라 3중량부를 혼합하여 고로슬래그의 활성화 특성을 검토하였다. The surface-modified blast furnace slag has an activity index of 50 parts by weight of cement, 50 parts by weight of blast furnace slag with a powderiness of 4,000 g/cm 3 to 4,800 g/cm 3, 245 parts by weight of fine aggregate, and carboxyl-based activation with respect to the standard formulation of 48.5 parts by weight of water. By mixing 3 parts by weight according to the blending ratio of the agent, the activation characteristics of the blast furnace slag were examined.
분말도(g/㎤)4 hours
Powder degree (g/cm3)
화합물(2) Glycol-based
Compound (2)
(2)글리콜계 화합물 : 디에틸렌글리콜(Note) (1) Amine compound: diethanolamine
(2) Glycol compound: diethylene glycol
상기 표 1에 따르면, 분쇄조제로서 본 발명 실시예 1~3에서와 같이 아민계 화합물과 글리콜계 화합물을 30:70~70:30의 중량비로 혼합하여 사용하는 경우, 최종 표면개질된 고로 슬래그의 4시간 분말도가 6,000g/㎤ 이상이고, 활성도지수도 3일 재령에 5% 이상 증가하였으며, 28일 재령에는 12% 이상 증가한 것을 확인할 수 있다.According to Table 1, when using a mixture of an amine-based compound and a glycol-based compound in a weight ratio of 30:70 to 70:30 as in Examples 1 to 3 of the present invention as a grinding aid, the final surface-modified blast furnace slag It can be seen that the powderiness for 4 hours was 6,000g/cm3 or more, and the activity index increased by 5% or more at the age of 3 days, and increased by 12% or more at the age of 28 days.
그러나, 분산조제로 처리하지 않은 비교예 1의 고로슬래그나 아민계 화합물로만 처리한 비교예 2의 고로슬래그는 4시간 분말도가 6,000g/㎤에 미치지 못하는 결과를 나타냈다. However, the blast furnace slag of Comparative Example 1 not treated with a dispersing aid or the blast furnace slag of Comparative Example 2 treated only with an amine-based compound showed a result that the powderiness did not reach 6,000 g/cm 3 for 4 hours.
또한, 글리콜계 화합물로만 처리한 비교예 3의 고로슬래그는 4시간 분말도가 6,600g/㎤으로 향상되었으나, 활성도지수 값이 무처리와 유사한 정도로 나타나는 것으로 보아 반응을 위한 비표면적이 증가하였음에도 반응성의 향상이 크지 않은 것으로 나타났다. In addition, the blast furnace slag of Comparative Example 3 treated with only glycol-based compounds improved the powderiness to 6,600 g/cm 3 for 4 hours, but the activity index value appeared to be similar to that of no treatment. The improvement was not found to be significant.
실시예 : 그라우트 조성물 제조Example: Preparation of grout composition
다음 표 3과 같은 구체 조성을 혼합하여 그라우트 조성물을 제조하였다. 즉, 표면개질된 고로 슬래그, 탈황석고, 고칼슘 플라이애시, 산화칼슘 및 수산화칼슘을 표 3의 조성대로 혼합한 혼합물 100중량%에 대하여 물을 40%의 중량비로 혼합하여 그라우트 조성물을 제조하였다. A grout composition was prepared by mixing the specific compositions shown in Table 3 below. That is, the surface-modified blast furnace slag, desulfurized gypsum, high calcium fly ash, calcium oxide, and calcium hydroxide were mixed in a weight ratio of 40% to 100% by weight of a mixture according to the composition of Table 3 to prepare a grout composition.
실험예 2 : 그라우트 조성물의 물성 측정Experimental Example 2: Measurement of physical properties of grout composition
상기 제조된 각 그라우트 조성물의 물성을 다음 표 2에 따라 측정하였으며, 그 결과를 다음 표 3에 나타내었다. The physical properties of each of the prepared grout compositions were measured according to Table 2 below, and the results are shown in Table 3 below.
본 발명에 따른 배면 충진용 그라우트재의 적절한 물성은 유동성은 180mm 이상, pH 11 이하, 팽창률은 3% 이상, 압축강도는 재령별로 3일 재령 7MPa 이상, 7일 재령 20MPa 이상, 28일 재령 30MPa 이상이 요구된다. The proper physical properties of the grout material for backfilling according to the present invention include fluidity of 180 mm or more, pH of 11 or less, expansion rate of 3% or more, and compressive strength of 7 MPa or more for 3 days, 20 MPa or more for 7 days, and 30 MPa or more for 28 days. Required.
중량부unit:
Parts by weight
슬래그(1) blast furnace
Slag (1)
(3) High Calcium Fly Ash
(3)
(mm)liquidity
(mm)
(%)Expansion rate
(%)
(MPa)Compressive strength
(MPa)
(2) 탈황 석고 : 분말도 3,800g/㎤인 것임.
(3) 고칼슘 플라이애시 : 분말도 4,000g/㎤인 것임. (1) Blast furnace slag: Examples 4 to 6 were prepared according to Examples 1 to 3, respectively. Comparative Examples 4 to 6 are those prepared according to Comparative Examples 1 to 3, respectively.
(2) Desulfurized gypsum: The powder is 3,800g/cm3.
(3) High calcium fly ash: 4,000g/cm3 of powder.
상기 표 3의 결과를 참조하면, 본 발명과 같이 아민계 화합물과 글리콜계 화합물로 이루어진 분쇄조제로 표면개질되어 분말도 6,000g/㎤ 이상 8,000g/㎤ 미만의 표면개질된 고로 슬래그를 사용한 그라우트 조성물의 경우 초기 강도 및 장기 강도가 우수하고 pH 11 이하의 저알칼리성 특성을 나타내는 것을 확인하였다.Referring to the results of Table 3, as in the present invention, a grout composition using surface-modified blast furnace slag having a powderiness of 6,000 g/cm 3 or more and less than 8,000 g/cm 3 by surface modification with a grinding aid consisting of an amine compound and a glycol compound In the case of, it was confirmed that the initial strength and long-term strength were excellent, and the low-alkali property of pH 11 or less was shown.
그러나, 아무 것도 처리하지 않은 분말도 4,400g/㎤인 비교예 4의 고로슬래그를 사용한 그라우트 조성물의 경우 초기 압축강도가 떨어지고, 아민계 화합물이나 글리콜계 화합물로만 표면개질시킨 고로슬래그의 경우 유동성이 떨어지거나, 초기 강도는 향상될지라도 저알칼리 특성을 가지지 못하는 것으로 나타났다. However, in the case of the grout composition using the blast furnace slag of Comparative Example 4, which is 4,400 g/cm 3 of powder without any treatment, the initial compressive strength is lowered, and in the case of the blast furnace slag surface-modified only with an amine compound or a glycol compound, the fluidity is poor. Or, although the initial strength was improved, it was found that it did not have low alkali properties.
이러한 결과로부터, 배면 충진용 그라우트재의 초기 강도의 확보와 저알칼리성의 조성물을 제공하기 위해서는 본 발명과 같은 조성으로 이루어진 분쇄조제를 이용하여 분말도가 조절된 표면개질된 고로슬래그의 사용이 필수적임을 확인할 수 있다. From these results, it was confirmed that in order to secure the initial strength of the grout material for backfilling and to provide a low-alkali composition, the use of surface-modified blast furnace slag with controlled powderiness using a pulverizing aid composed of the same composition as the present invention is essential. I can.
Claims (7)
상기 분쇄조제와 물의 혼합물을 고로슬래그 중량에 대하여 0.1~ 0.5 중량%로 첨가하여 3~4시간 동안 분쇄시켜 고로슬래그의 표면을 개질시키는 단계를 거쳐 제조된 6,000g/㎤ 이상 8,000g/㎤ 미만의 분말도를 가지는 표면개질된 고로 슬래그.An amine compound: mixing a grinding aid consisting of a glycol compound in a weight ratio of 30 to 70:70 to 30 with water in a weight ratio of 30:70 to 50:50, and
6,000 g/cm 3 or more and less than 8,000 g/cm 3 prepared through the step of modifying the surface of the blast furnace slag by adding the mixture of the pulverizing aid and water in an amount of 0.1 to 0.5% by weight based on the weight of the blast furnace slag and pulverizing for 3 to 4 hours. Surface-modified blast furnace slag with fineness.
상기 아민 화합물은 디에탄올아민(Diethanolamine), 트리에탄올아민(Triethanol amine), 및 트리이소프로판올 아민(Triisopropanol Amine)으로 이루어진 그룹으로부터 선택되는 1종 이상이며,
상기 글리콜 화합물은 디에틸렌글리콜(DIETHYLENE GLYCOL), 모노에틸렌글리콜(MONO-ETHYLENE GLYCOL), 및 프로필렌글리콜(Propylene Glycol)로 이루어진 그룹으로부터 선택되는 1종 이상인 것인 표면개질된 고로 슬래그. The method of claim 1,
The amine compound is at least one selected from the group consisting of diethanolamine, triethanol amine, and triisopropanol amine,
The glycol compound is a surface-modified blast furnace slag that is at least one selected from the group consisting of diethylene glycol (DIETHYLENE GLYCOL), monoethylene glycol (MONO-ETHYLENE GLYCOL), and propylene glycol (Propylene Glycol).
상기 배면 충진용 그라우트 조성물은 pH 11 이하의 저알칼리성인 것을 특징으로 하는 배면 충진용 그라우트 조성물.40-50% by weight of surface-modified blast furnace slag of 6,000g/cm3 or more and less than 8,000g/cm3 of powder, 40-50% by weight of desulfurized gypsum with a powder of 2,800-3,800g/cm3, and high calcium of 3,200-4,000g/cm3 As a rear filling grout composition comprising 3 to 5% by weight of fly ash, 1 to 3% by weight of calcium oxide, and 2 to 5% by weight of calcium hydroxide,
The rear filling grout composition is a rear filling grout composition, characterized in that the low alkalinity of pH 11 or less.
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