KR20020082320A - Cement Admixture for high strength, shrinkage-reducing and cold-construction, and cement composite incorporating the admixture - Google Patents

Cement Admixture for high strength, shrinkage-reducing and cold-construction, and cement composite incorporating the admixture Download PDF

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KR20020082320A
KR20020082320A KR1020010021565A KR20010021565A KR20020082320A KR 20020082320 A KR20020082320 A KR 20020082320A KR 1020010021565 A KR1020010021565 A KR 1020010021565A KR 20010021565 A KR20010021565 A KR 20010021565A KR 20020082320 A KR20020082320 A KR 20020082320A
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cement
admixture
weight
concrete
strength
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KR100508207B1 (en
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박응모
문경주
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문경주
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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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C04B22/142—Sulfates
    • C04B22/148—Aluminium-sulfate
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/10—Acids or salts thereof containing carbon in the anion
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/12—Acids or salts thereof containing halogen in the anion
    • C04B22/126—Fluorine compounds, e.g. silico-fluorine compounds
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/26—Carbonates
    • C04B14/28—Carbonates of calcium
    • 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
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08—Flue dust, i.e. fly ash
    • 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
    • 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
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]
    • 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
    • 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
    • C04B28/08—Slag cements
    • 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

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

Abstract

PURPOSE: Provided are a cement admixture with high strength, low shrinkage and low temperature application, and a cement composition with much improved initial strength, longtime strength and durability compared with portland cement by mixing cement with the prepared admixture. CONSTITUTION: The admixture comprises 75-100wt.% Al2(SO4)3 as a main material, 0-10wt.% of Na2CO3, 0-10wt.% of NaAlO2, 0-25wt.% of CaCl2, 0-15wt.% of limestone, and 0-5wt.% of magnesium fluosilicate, where the all materials have a specific surface area of 2000cm¬2/g or more, except limestone with a specific surface area of 5000cm¬2/g or more. Also, the cement admixture is prepared by adding 1-10wt.% of the prepared admixture to conventional cement such as portland cement, high early-strength portland cement, fly ash cement or blast furnace slag cement.

Description

고강도, 수축저감, 저온시공이 가능한 시멘트 혼화재 및 이를 함유한 시멘트 조성물 {Cement Admixture for high strength, shrinkage-reducing and cold-construction, and cement composite incorporating the admixture}Cement admixture for high strength, shrinkage reduction and low temperature construction and cement composition containing same {Cement Admixture for high strength, shrinkage-reducing and cold-construction, and cement composite incorporating the admixture}

본 발명은 고강도, 무수축, 저온시공이 가능한 시멘트 혼화재 및 이를 함유한 시멘트 조성물에 관한 기술로서 더욱 자세하게는 황산알루미늄, 탄산나트륨, 알루민산나트륨 및 석회석 미분말, 규산화마그네슘을 적당한 비율로 혼합하여 제조한 혼화재를 보통포틀랜트 시멘트에 1∼10% 첨가함으로서 보통포틀랜트 시멘트의 초기강도와 장기강도를 월등하게 향상시키고 수축저감 및 저온시공이 가능하며 내구성을 월등히 향상시킬 수 있는 시멘트 혼화재의 제조에 관한 기술이다.The present invention relates to a cement admixture capable of high strength, non-shrinkage and low temperature construction, and a cement composition containing the same. By adding 1 ~ 10% of admixtures to ordinary portland cement, it is possible to improve the initial strength and long-term strength of ordinary portland cement significantly, and to reduce the shrinkage and low temperature construction, and to manufacture cement admixtures that can greatly improve durability. to be.

본 발명의 혼화재는 모르타르 또는 콘크리트의 제반 물성을 상기와 같이 향상시키므로 콘크리트 제품용 및 일반 토목공학 및 건축 구조물용으로도 광범위하게 사용된다.Since the admixture of the present invention improves the physical properties of mortar or concrete as described above, it is widely used for concrete products and general civil engineering and building structures.

현재 일반적으로 사용되고 있는 포틀랜드 시멘트는 실리카, 알루미나 및 석회를 주성분으로 하는 원료를 적당한 비율로 충분히 혼합하여, 그 일부가 용융되어 소결된 클링커에 적당량의 석고를 첨가하여 분말로 한 것이며 조강포틀랜드시멘트는 3CaO· SiO2의 함유량을 보통포틀랜트 시멘트의 3CaO · SiO2함유량 54% 정도보다 약 8% 높이고 비표면적을 보통포틀랜트 시멘트의 3300㎠/g 정도보다 약 1300㎠/g 이상 높이어 제조한 것으로서, 보통포틀랜드 시멘트의 7일강도가 3일만에 발현되므로 공기단축을 요하는 공사는 물론 2차제품 적용시 몰드회전율을 향상시킬 수 있는 장점이 있다. 그러나 조강시멘트의 제조시 분쇄시간의 증가에 따른 생산량의 감소와 원가증가의 원인으로 인하여 범용화되지 않고 있는 실정이다.Portland cement, which is currently commonly used, is a powder made by mixing a sufficient amount of raw materials mainly composed of silica, alumina, and lime in an appropriate ratio, and adding a portion of gypsum to a molten and sintered clinker, and the crude steel portland cement is 3CaO. , the content of SiO 2 as ordinary portland cement manufactured of 3CaO · SiO 2 content of about 8% to increase the specific surface area of usually at least about 1300㎠ / g than about 3300㎠ / g of portland cement than 54% of nopyieo, usually Since the 7-day strength of Portland Cement is expressed in 3 days, there is an advantage of improving mold turnover when applying secondary products as well as construction requiring air shortening. However, the production of crude steel cement has not been generalized due to the reduction of the production amount and the increase of cost due to the increase of the grinding time.

따라서 보통포틀랜트 시멘트에 혼화재를 첨가하여 조강시멘트를 제조할 수있다면 시멘트 제조역사에서 획기적인 발명으로 될 것이다. 본 연구는 이 점에 착안하여 3년동안의 꾸준한 연구를 실행하여 본 혼화재를 발명하였으며 이를 보통포틀랜트시멘트 조성물에 첨가하여 그 물성을 검토하였는바, 보통포틀랜드시멘트에 비하여 매우 우수하며 조강포틀랜드시멘트와 거의 동등한 성질을 나타내었다.Therefore, if the crude cement can be prepared by adding admixtures to ordinary portland cement, it will be a revolutionary invention in cement manufacturing history. Based on this point, this research was carried out for 3 years of continuous research to invent the admixture, which was added to ordinary portant cement composition and examined for its physical properties. It is much superior to ordinary portland cement and is better than crude portland cement. Almost equivalent properties.

본 발명으로 제조한 혼화재를 첨가한 시멘트의 초기강도는 보통포틀랜트시멘트보다 1.4∼1.6배이며 장기강도도 매우 우수하기 때문에 공기단축을 요하는 공사는 물론 2차제품 적용시 몰드회전율을 향상시킬 수 있으며 특히 증기양생시 고강도를 발현할 수 있다. 따라서 일반적인 용도 즉, 범용성을 갖춘 시멘트로의 대량 활용도 기대할 수 있다.The initial strength of cement with the admixture prepared by the present invention is 1.4-1.6 times higher than that of ordinary portant cement, and the long-term strength is also very good, so that the mold rotation rate can be improved when applying secondary products as well as construction requiring air shortening. In particular, it can express high strength during steam curing. Therefore, it can also be expected to use a large amount of general purpose, that is, as a general purpose cement.

또한, 본 발명으로 제조한 혼화재의 적당량 첨가에 따른 시멘트는 보통포틀랜드시멘트에 비하여 내화학성이 매우 우수한데 이는 보통 포틀랜드 시멘트 중의 규산 3석회나 규산 2석회는 수화하면서 다량의 Ca(OH)2를 생성시키는데 이의 존재는 화학적 침식에 대한 저항성 면에서는 마이너스적인 역활을 한다. 그러나 본 발명의 혼화재를 적당량 첨가하면 보통포틀랜트 시멘트의 수화반응에서 생성되는 Ca(OH)2와 수화반응하여 모세관 공극을 충진하는 수 ㎛의 침상결정형인 에틀링가이트를 위주로 하는 수화물을 다량 생성하여 시멘트 경화체내의 공극 감소작용으로 경화체를 치밀하게 할뿐만 아니라 Ca(OH)2량을 일부 감소하기 때문에 각종의 염류, 특히 황산염이나 해수작용에 대한 저항성이 우수하다. 따라서 해상구조물, 항만건축, 간척지 공사와 생활폐수를 취급하는 도시하부 구조물 및 공장폐수로, 폐기물의 고화재 등에 사용될 수 있으며, 농어촌의 관개수로용 및 어초 등 수중 및 해중 구조물에 매우 적합하다.In addition, the cement according to the addition of a suitable amount of the admixture prepared by the present invention has excellent chemical resistance compared to the ordinary portland cement, which usually generates a large amount of Ca (OH) 2 while hydrated tricalcium silicate or dibasic silicate lime in portland cement. Its presence plays a negative role in resistance to chemical erosion. However, when an appropriate amount of the admixture of the present invention is added, a large amount of hydrates are formed around ettlingite, which is a needle-shaped crystal form of several μm filling the capillary pores by hydration with Ca (OH) 2 generated in the hydration reaction of ordinary portland cement. The pore-reducing action in the cement hardened body not only makes the hardened body compact but also partially reduces the amount of Ca (OH) 2, so it is excellent in resistance to various salts, in particular sulfate or seawater. Therefore, it can be used for marine structures, harbor construction, reclaimed land construction, urban substructures and factory wastewater, waste fires, etc., and is suitable for underwater and underwater structures such as irrigation canals and reefs in farming and fishing villages.

또한 본 발명으로 제조한 혼화재의 적당량 첨가에 따른 시멘트는 저온에서도 초기강도의 증진 효과가 현저하게 크다고 하는 우수한 특성을 가지고 있다. 바깥기온이 5℃이하인 한냉기에 콘크리트 공사를 하는 한중 콘크리트를 시공하는데 있어 보통포틀랜드 시멘트를 이용할 경우 콘크리트의 동해에 대한 저항성을 확보할 수 있는 압축강도(일반적으로 30∼50kgf/㎠로 되어있음)에 이르기까지의 초기양생기간중에 동해를 받지 않도록 가온양생 및 보온양생을 해야하는데 본 발명에 의한 혼화재를 함유한 시멘트를 이용할 경우 초기 강도 증진효과가 크기 때문에 초기양생 기간 중의 보온양생 혹은 가온양생을 생략 또는 경감할 수 있다.In addition, the cement according to the addition of a suitable amount of the admixture prepared by the present invention has an excellent characteristic that the effect of increasing the initial strength is significantly greater even at low temperatures. In case of using ordinary portland cement for concrete construction in concrete with cold temperature below 5 ℃, the compressive strength (typically 30 ~ 50kgf / ㎠) that can secure the resistance to the east sea of concrete is used. Warm curing and warming curing should be performed so as not to receive the East Sea during the initial curing period. However, when the cement containing the admixture according to the present invention is used, the warming curing or warming curing during the initial curing period is omitted or I can alleviate it.

또한 본 발명으로 제조한 혼화재의 적당량 첨가에 따른 시멘트는 침상의 팽창성 광물인 에트링가이트를 모세관 공극내에 다량 생성하고, 이에 의해 다량의 자유수를 결정수로 고정시켜 모르타르 및 콘크리트 건조수축을 보상할 수 있다.In addition, the cement according to the appropriate amount of admixture prepared by the present invention generates a large amount of edringite, a needle-like expandable mineral in the capillary pores, thereby fixing a large amount of free water with crystallized water to compensate for mortar and concrete dry shrinkage. Can be.

상기와 같이, 본 발명에 의한 혼화재는 보통포틀랜드 시멘트에 우수한 성질을 부여하면서 특별한 소성과정을 필요치 않고 단순 분쇄 혼합공정에 의하여 제조가 가능하며 시멘트 중량에 단지 1∼10%, 가장 바람직하게는 4∼6%의 사용으로 상기와 같은 우수한 성질을 발현시킬 수 있기 때문에 적은 투자비로 물성이 우수한 콘크리트 제품을 저렴하게 제조할 수 있다.As described above, the admixture according to the present invention can be manufactured by a simple pulverizing mixing process without imparting a special firing process while giving excellent properties to ordinary portland cement, only 1 to 10% by weight of cement, most preferably 4 to Since the use of 6% can express such excellent properties, it is possible to cheaply manufacture concrete products having excellent properties at a low investment cost.

따라서, 본 발명에 의한 혼화재를 보통포틀랜트 시멘트에 1∼10% 혼입함으로서 보통포틀랜트 시멘트의 초기강도와 장기강도를 월등하게 향상시키고 수축저감 및 저온시공이 가능하게 하며 내구성(내염성, 내산성)을 월등히 향상시킬 수 있는 시멘트 혼화재의 제조에 관한 기술을 제공하는데 그 목적이 있다.Therefore, by admixing the admixture according to the present invention in 1-10% of ordinary portland cement, the initial strength and long-term strength of the ordinary portland cement are greatly improved, shrinkage reduction and low temperature construction are possible, and durability (flame resistance, acid resistance) is improved. The purpose is to provide a technique for the production of cement admixtures that can be significantly improved.

도1은 본 발명의 혼화재를 함유한 시멘트와 시중에서 판매되고 있는 보통포틀랜트 시멘트 및 조강포틀랜드 시멘트의 압축강도를 비교한 그래프.1 is a graph comparing the compressive strength of cement containing the admixture of the present invention and ordinary portland cement and crude steel portland cement on the market.

도2는 본 발명의 혼화재를 함유한 시멘트와 시중에서 판매되고 있는 보통포틀랜트 시멘트를 저온(0℃)에서 양생하여 압축강도를 비교한 그래프.Figure 2 is a graph comparing the compressive strength by curing the cement containing the admixture of the present invention and commercially available ordinary portland cement at low temperature (0 ℃).

도3은 본 발명의 혼화재를 함유한 시멘트와 시중에서 판매되고 있는 보통포틀랜트 시멘트의 내산성을 비교한 그래프.Figure 3 is a graph comparing the acid resistance of the cement containing the admixture of the present invention and ordinary portland cement on the market.

도4는 본 발명의 혼화재를 함유한 시멘트를 이용하여 제작한 콘크리트와 시중에서 판매되고 있는 보통포틀랜트 시멘트를 이용하여 제작한 콘크리트의 압축강도를 비교한 그래프.Figure 4 is a graph comparing the compressive strength of the concrete produced by using the cement containing the admixture of the present invention and the concrete produced using commercially available portland cement on the market.

도5는 본 발명의 혼화재를 함유한 시멘트를 이용하여 제작한 콘크리트와 시중에서 판매되고 있는 보통포틀랜트 시멘트를 이용하여 제작한 콘크리트의 건조수축을 비교한 그래프.Figure 5 is a graph comparing the dry shrinkage of the concrete produced by using the cement containing the admixture of the present invention and concrete produced using a commercially available portland cement on the market.

상기 목적을 달성하기 위한 본 발명에 따른 혼화재의 조성물은 황산알루미늄 75∼100중량%와 탄산나트륨 0∼10중량%, 알루민산나트륨, 0∼10중량%, 염화칼슘 0∼25중량%, 석회석 미분말 0∼15중량%, 규불화마그네슘 0∼5%를 포함하며 석회석 미분말을 제외한 다른재료는 2,000㎠/g 이상의 비표면적을 갖고 있는 것을 특징으로 한다. 주재료인 황산알루미늄은 무수황산알루미늄 혹은 결정수를 함유한 황산알루미늄으로서 공업용(소위 17% 황산알루미늄- 17% Al2O3, 또는 약 57% Al(SO4)2)으로 시판되고 있는 것을 사용할 수 있으며 그 안에 포함된 불순물은 어떠한 영향도 주지 아니한다. 소량 첨가되는 탄산나트륨, 알루민산나트륨, 염화칼슘 및 석회석 미분말, 규불화마그네슘 또한 공업용으로 시판되고 있는 것을 사용할 수 있다.Composition of the admixture according to the present invention for achieving the above object is 75 to 100% by weight of aluminum sulfate and 0 to 10% by weight of sodium carbonate, 0 to 10% by weight of sodium aluminate, 0 to 25% by weight of calcium chloride, 0 to 25% of limestone fine powder 15 wt%, magnesium silicate includes 0-5%, and other materials except fine limestone powder have a specific surface area of 2,000 cm2 / g or more. Aluminum sulfate as the main material is anhydrous aluminum sulfate or aluminum sulfate containing crystal water, which is commercially available (so-called 17% aluminum sulfate-17% Al 2 O 3 , or about 57% Al (SO 4 ) 2 ). And impurities contained in it have no effect. Sodium carbonate, sodium aluminate, calcium chloride and fine limestone powder, and magnesium silicate which are added in small amounts may also be commercially available.

본 발명에 따른 혼화재의 가장 중요한 것은 초기 및 장기재령에서 고강도를 발현시킬 수 있다는 점으로서 그 원인은 혼화재중의 황산알루미늄, 탄산나트륨, 알루민산나트륨, 염화칼슘은 수중에서 이온으로 해리되어 시멘트의 수화반응을 촉진할 뿐만 아니라 특히 황산알루미늄이 시멘트의 수화반응에서 생성되는 수산화칼슘과 반응하여 Calcium Sulphur Aluminate(3CaO · Al2O3. 3CaSO4· 32H2O, ettingite)를 위주로 하는 수화물을 생성하여 치밀한 골격구조를 형성하는데 있다.비표면적이 5000㎠/g 이상인 석회석 미분말을 혼입하면 초기강도가 5∼10% 정도 증가된다. 이것은 시멘트의 수화반응에서 생성되는 공극을 충전시켜 밀실도를 증가시킬 뿐만 아니라 그 중의 일부는 에트링가이트 중의 황산염을 치환하여 결정체를 형성하는 동시에 치환된 황산염이 시멘트의 반응을 촉진하기 때문이다. 규불화마그네슘은 황산알루미늄, 탄산나트륨, 황산나트륨의 급격한 응결 및 경화를 방지하고 콘크리트에 유동성을 확보할 수 있기 때문에 레디믹스드콘크리트에 유용하다.The most important thing of the admixture according to the present invention is that it can express high strength in early and long-term age, and the cause is that aluminum sulfate, sodium carbonate, sodium aluminate and calcium chloride in the admixture are dissociated into ions in water to perform the hydration reaction of cement. In addition, the aluminum sulfate reacts with calcium hydroxide, which is produced in the hydration reaction of cement, to form a hydrate based on Calcium Sulfur Aluminate (3CaOAl 2 O 3 .3CaSO 4 32H 2 O, ettingite). Incorporation of limestone fine powder with a specific surface area of 5000 cm2 / g or more increases the initial strength by 5-10%. This is due to the filling of the voids generated in the hydration of the cement to increase the degree of closedness, some of them to replace the sulfate in the ettringite to form crystals, while the substituted sulfate promotes the reaction of the cement. Magnesium silicate is useful for ready-mixed concrete because it prevents the rapid condensation and hardening of aluminum sulfate, sodium carbonate and sodium sulfate and ensures fluidity in concrete.

이하 본 발명을 실시예에 의거하여 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail with reference to Examples.

(실시 예1-3)(Example 1-3)

본 발명에 따른 혼화재의 조성물은 표1과 같다.The composition of the admixture according to the present invention is shown in Table 1.

상기와 같은 혼화재를 함유한 시멘트의 물리성능을 검증하기 위하여, 혼화재와 보통포틀랜트 시멘트를 중량비로 5%와 95% 혼합하여 제조한 시멘트인 H-OPC(본발명의 실시예), 시중에서 판매되고 있는 보통포틀랜트시멘트(OPC), 조강포틀랜트시멘트(ESPC)와 압축강도 특성을 비교하기 위하여 실험을 실시하였으며 그 결과를 표2와 도1에 나타내었다.In order to verify the physical performance of the cement containing the admixture as described above, H-OPC (an embodiment of the present invention), which is a cement manufactured by mixing the admixture and the ordinary port cement in 5% and 95% by weight, commercially available Experiments were conducted to compare the compressive strength characteristics of the ordinary port cement (OPC) and the crude steel port cement (ESPC), and the results are shown in Table 2 and FIG.

표2에서 W/C는 시멘트(C)에 대한 혼합수(W)의 중량비를 나타내고, C/S중의 C는 시멘트를 나타내며 S는 표준사를 나타낸다. 표2 및 도1에 나타낸 것과 같이, 본 발명으로 제조한 혼화재를 함유한 H-OPC는 초기재령인 3일의 압축강도에서 OPC보다 약 43∼60% 증가하였고 ESPC와 거의 동등하거나 그 이상으로 나타났다. 7일의 압축강도에서도 OPC는 물론 ESPC보다도 약 30%이상 우수하게 나타났으며 28일 압축강도도 OPC 및 ESPC에 비하여 월등하게 높음을 확인할 수 있다. 따라서 본 발명에 의한 혼화재를 함유한 시멘트는 보통포틀랜드시멘트에 비하여 강도가 매우 우수하며 조강포틀랜드시멘트와 거의 동등 이상의 물성 발현이 가능하므로 콘크리트 및 콘크리트 2차제품으로서의 대량 활용이 기대된다. 그러나 실시예 3에 의한 조성을 가진혼화재는 철근콘크리트에 이용될 시 염화칼슘에 의한 철근 부식을 초래할 수 있으므로 콘크리트 2차제품 및 무근콘크리트에 이용하는 것이 바람직하다.In Table 2, W / C represents the weight ratio of mixed water (W) to cement (C), C in C / S represents cement, and S represents standard yarn. As shown in Table 2 and FIG. 1, H-OPC containing the admixture prepared according to the present invention increased about 43-60% of OPC at almost 3 days of compressive strength, which was almost equivalent to or greater than ESPC. . The 7-day compressive strength was about 30% better than the OPC as well as the ESPC, and the 28-day compressive strength was significantly higher than the OPC and ESPC. Therefore, the cement containing the admixture according to the present invention is very excellent in strength compared to ordinary portland cement, and can be expressed in physical properties almost equal to that of crude steel portland cement, so it is expected to be utilized in large quantities as concrete and concrete secondary products. However, since the admixture having the composition according to Example 3 may cause reinforcing corrosion by calcium chloride when used in reinforced concrete, it is preferable to use it in concrete secondary products and bare concrete.

본 발명에 따른 혼화재를 함유한 시멘트의 저온에서의 강도 발현 성능 및 내산성을 검증하기 위하여, 혼화재(상기의 실시예 2)와 보통포틀랜트 시멘트를 중량비로 6%와 94% 혼합 제조하여, 시중에서 판매되고 있는 보통포틀랜트 시멘트와 비교 실험을 실시하였다. 그 결과를 표3과 도2, 도3에나타내었다. 여기에서 내산성 실험은 20℃에서 28일 양생 후 실시하였다.In order to verify the strength development performance and acid resistance of the cement containing the admixture according to the present invention at low temperatures, by mixing 6% and 94% by weight of the admixture (Example 2 above) and ordinary portland cement, A comparative experiment was conducted with the common portland cement sold. The result is shown in Table 3, FIG. 2, and FIG. Here, the acid resistance test was performed after curing at 20 ° C. for 28 days.

표 3과 같이 본 발명은 경화체의 기본적 성능의 손실없이 저온시에 있어서 초기강도를 발현시킬 수 있어 저온 시공용 모르타르 및 콘크리트 혼화제로서 우수한 성능을 가졌다는 것을 알 수 있다. 또한 내산성이 보통포틀랜드 시멘트에 비하여 매우 우수하다는 것을 알 수 있다.As shown in Table 3, the present invention can express the initial strength at low temperature without loss of the basic performance of the cured product, and it can be seen that it had excellent performance as a mortar and concrete admixture for low temperature construction. It can also be seen that the acid resistance is very good compared to ordinary portland cement.

(실시예 4)(Example 4)

본 발명에 의한 혼화재를 함유한 시멘트 조성물의 물리성능을 검증하기 위하여, 표 4와 같이 제조한 혼화재와 보통포틀랜트 시멘트를 중량비로 5%와 95% 혼합하여 제조한 시멘트인 H-OPC(본발명)와 시중에서 판매되고 있는 보통포틀랜트 시멘트(OPC)를 이용하여 20℃에서 콘크리트를 제조 및 양생하여 슬럼프 및 압축강도를 측정하였다. 표 5에 나타낸바와 같은 배합으로 콘크리트 공시체를 제작하여 그 결과를 표 6 및 그림 4에 나타내었다. 또한 본 발명에 의한 혼화재를 함유한 콘크리트의 수축특성을 검증하기 위하여, 혼화재를 보통포틀랜트 시멘트와 5%와 95% 비율로 혼합하여 제조한 시멘트인 H-OPC(본발명)와 시중에서 판매되고 있는 보통포틀랜트 시멘트(OPC)를 이용하여 제조한 콘크리트의 조성물을 탈형 후 20℃에서 건조시켜 재령에 따른 수축량을 측정하였다. 그 결과를 표 7 및 그림 5에 나타내었다.In order to verify the physical performance of the cement composition containing the admixture according to the present invention, H-OPC is a cement prepared by mixing 5% and 95% by weight of the admixture and ordinary portland cement prepared as shown in Table 4 ) And commercially available commercial portland cement (OPC) were used to prepare and cure concrete at 20 ° C to measure slump and compressive strength. Concrete specimens were prepared with the formulation as shown in Table 5 and the results are shown in Table 6 and Figure 4. In addition, in order to verify the shrinkage characteristics of the concrete containing the admixture according to the present invention, the admixture is commercially available with H-OPC (invention), which is a cement manufactured by mixing the admixture with ordinary port cement at a ratio of 5% and 95%. After the demoulding, the composition of the concrete prepared by using ordinary portland cement (OPC) was dried at 20 ° C. to measure the shrinkage according to age. The results are shown in Table 7 and Figure 5.

표4에서 S는 잔골재(강모래, 비중 2.54)를 나타내며 G는 굵은골재(쇄석, 비중 2.62)로서 최대치수가 25mm인 것을 사용하였다.In Table 4, S represents fine aggregate (steel sand, specific gravity 2.54) and G is coarse aggregate (crushed stone, specific gravity 2.62), and the largest dimension is used.

표6에 나타낸 것과 같이, 본 발명으로 제조한 혼화재를 함유한 콘크리트는 OPC만을 첨가한 콘크리트에 비해 비빔직후 슬럼프가 약 2cm 적게 나타났는데, 이는 혼화재가 물을 급격히 흡수하기 때문이다. 그러나 시간의 경과에 따른 슬럼프의 변화는 혼화재에 함유된 규불화마그네슘으로 인해 급격한 슬럼프 감소를 막을 수 있어 향후 레미콘으로 사용될 경우 큰 문제는 없는 것으로 나타났다. 또한 초기강도 및 장기강도가 OPC만을 이용한 콘크리트에 비해 월등히 크게 나타났다. 초기재령인 1일 및 3일 압축강도는 OPC만을 이용한 콘크리트 보다 약 30∼40% 크게 나타났으며 7일의 압축강도에서도 약 30% 이상 우수하게 나타났다. 장기재령인 28일 및 90일의압축강도도 OPC만을 이용한 콘크리트에 비하여 월등하게 높음을 확인할 수 있었다.As shown in Table 6, the concrete containing the admixture prepared by the present invention showed about 2 cm less slump immediately after the beam than the concrete containing only OPC, because the adsorbent rapidly absorbs water. However, the change in slump over time can prevent the sudden slump decrease due to the magnesium fluoride contained in the admixture, so that it is not a big problem when used as a ready-mixed concrete in the future. In addition, the initial strength and long-term strength were significantly higher than those of OPC-only concrete. The initial compressive strengths of 1 and 3 days were about 30 ~ 40% greater than that of OPC-only concrete, and were better than about 30% even at 7 days of compressive strength. The long-term age of 28 and 90 days was also significantly higher than that of OPC-only concrete.

표7에 나타낸 것과 같이, 본 발명으로 제조한 혼화재를 함유한 콘크리트는 OPC만을 첨가한 콘크리트에 비해 수축량을 거의 50%이상 감소시킬 수 있어 기존 모르타르 및 콘크리트의 수축균열을 방지하는 효과를 얻을 수 있다.As shown in Table 7, the concrete containing the admixture prepared by the present invention can reduce the amount of shrinkage by more than 50% compared to the concrete added only OPC can obtain the effect of preventing the shrinkage cracking of the existing mortar and concrete .

한편, 실제로 1m×1m의 형틀에 본 발명의 혼화제를 첨가한 콘크리트를 타설한 결과 상기와 같이 건조 수축이 감소하여 균열이 발생하지 않음을 확인할 수 있었다.On the other hand, as a result of placing concrete in which the admixture of the present invention was added to the mold of 1m × 1m, it was confirmed that the drying shrinkage was reduced as described above, so that cracking did not occur.

본 발명에 의한 혼화재를 보통포틀랜트 시멘트에 1∼10% 혼입함으로서 콘크리트 또는 콘크리트 제품의 제조에 널리 일반적으로 사용할 수 있다.The admixture according to the present invention can be widely used in the production of concrete or concrete products by incorporating 1 to 10% of ordinary portland cement.

즉, 본 발명에 의한 혼화재를 함유하는 시멘트 조성물은 보통포틀랜드시멘트만을 사용한 조성물에 비하여 초기강도와 장기강도가 월등하게 높고, 수축을 월등히 감소시키며 내구성 및 저온시공이 성능이 뛰어난 시멘트 조성물의 제조가 가능하다. 따라서, 일반 토목 공학 및 건설 구조물에 관하여 작업기간을 단축할 수 있고, 저온에서도 시공이 가능하여 건설 작업의 효율 및 합리성을 향상시킬 수 있다. 또한 2차 제품에 관하여 이형 작업주기를 단축시킬 수 있고 생산성을 향상시킬 수 있다.That is, the cement composition containing the admixture according to the present invention has a significantly higher initial strength and long-term strength than the composition using ordinary portland cement, significantly reduces shrinkage, and can be manufactured with excellent durability and low temperature construction. Do. Therefore, the working period can be shortened with respect to general civil engineering and construction structures, and construction can be performed at low temperatures, thereby improving efficiency and rationality of construction work. It can also shorten the release cycle and improve productivity with respect to secondary products.

Claims (6)

황산알루미늄 75∼100중량%와 탄산나트륨 0∼10중량%, 알루민산나트륨 0∼10중량%, 염화칼슘 0∼25중량%, 석회석 미분말 0∼10중량%, 규불화마그네슘 0∼5중량%를 포함하는 것을 특징으로 하는 시멘트 혼화재 조성물.75 to 100% by weight of aluminum sulfate, 0 to 10% by weight of sodium carbonate, 0 to 10% by weight of sodium aluminate, 0 to 25% by weight of calcium chloride, 0 to 10% by weight of fine limestone powder, and 0 to 5% by weight of magnesium silicate Cement admixture composition, characterized in that. 제1항에 있어서, 위와 같은 방식으로 조성된 혼합물을 혼화재로서 시멘트에 1∼10중량%를 함유한 시멘트 조성물.The cement composition according to claim 1, wherein the mixture prepared in the above manner contains 1 to 10% by weight of cement as admixture. 제 1항에 있어서, 석회석 미분말(비표면적 5,000㎠/g 이상)을 제외한 재료의 비표면적이 2,000㎠/g 이상의 비표면적을 갖고 있는 것을 특징으로 하는 시멘트 혼화재 조성물.The cement admixture composition according to claim 1, wherein the specific surface area of the material excluding the fine limestone powder (specific surface area 5,000 cm 2 / g or more) has a specific surface area of 2,000 cm 2 / g or more. 제2항에 있어서, 시멘트가 보통포틀랜드시멘트, 조강포틀랜드시멘트, 플라이애쉬시멘트, 고로슬래그시멘트 중의 어느 한 종류인 것을 특징하는 하는 시멘트 조성물.3. The cement composition according to claim 2, wherein the cement is one of ordinary portland cement, crude steel portland cement, fly ash cement, and blast furnace slag cement. 제1항, 제3항에 기재된 혼화재를 함유한 시멘트 조성물에 필요에 따라서 혼화제 또는 혼화재를 배합하는 것을 특징으로 하는 레디믹스드콘크리트 제조방법.A method for producing ready-mixed concrete, wherein the cement composition containing the admixture according to claim 1 is blended as necessary. 제1항, 제3에 기재된 혼화재를 함유한 시멘트 조성물에 필요에 따라서 혼화제 또는 혼화재를 배합하는 것을 특징으로 하는 콘크리트 2차제품의 제조방법.A method for producing a concrete secondary product, comprising admixing a admixture or admixture as necessary to a cement composition containing the admixture according to claim 1 or 3.
KR10-2001-0021565A 2001-04-20 2001-04-20 Cement Admixture for high strength, shrinkage-reducing and cold-construction, and cement composite incorporating the admixture KR100508207B1 (en)

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KR100649446B1 (en) * 2006-05-08 2006-11-28 석성기업주식회사 A compositions of soil solidifier and soil structures using its compositions
KR100911721B1 (en) * 2008-09-30 2009-08-10 나종천 Compound, and mortar and concrete including the same
CN111039584A (en) * 2019-12-14 2020-04-21 浙江工业大学 Fine-grained tailing surface curing agent and application method thereof
KR102286956B1 (en) * 2020-11-09 2021-08-09 (주)자연과환경 Concrete block containing photocatalyst
KR102585351B1 (en) 2023-03-16 2023-10-06 주식회사 앨앤애프코리아 PPerformance improver for concrete structure and construction method using it

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
KR100649446B1 (en) * 2006-05-08 2006-11-28 석성기업주식회사 A compositions of soil solidifier and soil structures using its compositions
KR100911721B1 (en) * 2008-09-30 2009-08-10 나종천 Compound, and mortar and concrete including the same
CN111039584A (en) * 2019-12-14 2020-04-21 浙江工业大学 Fine-grained tailing surface curing agent and application method thereof
CN111039584B (en) * 2019-12-14 2022-03-15 浙江工业大学 Fine-grained tailing surface curing agent and application method thereof
KR102286956B1 (en) * 2020-11-09 2021-08-09 (주)자연과환경 Concrete block containing photocatalyst
KR102585351B1 (en) 2023-03-16 2023-10-06 주식회사 앨앤애프코리아 PPerformance improver for concrete structure and construction method using it

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