KR100310657B1 - Quick-hardening cement composition having high solidity - Google Patents
Quick-hardening cement composition having high solidity Download PDFInfo
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- KR100310657B1 KR100310657B1 KR1019990017276A KR19990017276A KR100310657B1 KR 100310657 B1 KR100310657 B1 KR 100310657B1 KR 1019990017276 A KR1019990017276 A KR 1019990017276A KR 19990017276 A KR19990017276 A KR 19990017276A KR 100310657 B1 KR100310657 B1 KR 100310657B1
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- 239000004568 cement Substances 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 239000011575 calcium Substances 0.000 claims abstract description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011398 Portland cement Substances 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 108010001779 Ancrod Proteins 0.000 claims abstract description 7
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 7
- 239000000378 calcium silicate Substances 0.000 claims abstract description 6
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 5
- 230000015271 coagulation Effects 0.000 claims abstract description 3
- 238000005345 coagulation Methods 0.000 claims abstract description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 17
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 9
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000004902 Softening Agent Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- -1 calcium sulfo aluminate Chemical class 0.000 abstract description 3
- 239000010440 gypsum Substances 0.000 abstract description 3
- 229910052602 gypsum Inorganic materials 0.000 abstract description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 2
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 2
- 239000004571 lime Substances 0.000 abstract description 2
- IKGXIBQEEMLURG-NVPNHPEKSA-N rutin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-NVPNHPEKSA-N 0.000 abstract 1
- 230000007774 longterm Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 235000012241 calcium silicate Nutrition 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011444 non-shrink grout Substances 0.000 description 1
- 239000011513 prestressed concrete Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- C04B28/14—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
- C04B28/16—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 anhydrite, e.g. Keene's 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
- 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
- C04B14/04—Silica-rich materials; Silicates
- C04B14/043—Alkaline-earth metal silicates, e.g. wollastonite
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Civil Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
본 발명은 고강도의 속경성 시멘트 조성물에 관한 것으로, 좀 더 상세하게는 고강도의 속경성 시멘트 조성물에 있어서, 칼슘설포알루미네이트(3CaOㆍ3Al2O3ㆍ CaSO4) 및 칼슘실리케이트(2CaOㆍSiO2)를 주성분으로 하는 아윈계 클린커 35 내지 50중량%, 보통 포틀랜드 시멘트 25 내지 35중량%, 무수석고 10 내지 25중량%와, 소석회 5 내지 10중량%로 이루어진 혼합시멘트 100중량부에 대하여 멜라민계 고유동화제 0.1 내지 1중량부 및 응결지연제로서 구연산 0.1 내지 1중량부를 포함하는 고강도의 속경성 시멘트 조성물에 관한 것이다. 본 발명의 조성물은 초기강도 및 후기강도에 있어서도 우수한 압축강도를 나타내고 있어 시급성을 요구하는 구조물의 보수에 유용하게 사용될 수 있다.The present invention relates to a relates to a genus rigid cement composition of high strength, more specifically, in a rigid cement composition of high strength, calcium sulfo aluminate (3CaO and 3Al 2 O 3 and CaSO 4) and calcium silicate (2CaO and SiO 2 Melin-based based on 100 parts by weight of the mixed cement consisting of 35 to 50% by weight of the Arwin-based clinker, usually 25 to 35% by weight of Portland cement, 10 to 25% by weight of gypsum and 5 to 10% by weight of lime A high strength fast cement composition comprising 0.1 to 1 parts by weight of a high fluidizing agent and 0.1 to 1 parts by weight of citric acid as a coagulation delay agent. The composition of the present invention exhibits excellent compressive strength even in the initial strength and the late strength, and can be usefully used for the repair of structures requiring urgent need.
Description
본 발명은 고강도의 속경성 시멘트 조성물에 관한 것으로, 좀 더 상세하게는 구조물의 보수시에 긴급성이 요구되는 경우에 사용되는 속경성을 지니면서 고강도를 함께 갖는 시멘트 조성물에 관한 것이다.The present invention relates to a high-strength fast cement composition, and more particularly to a cement composition having a high strength and high strength used when urgency is required in repairing the structure.
속경성 시멘트는 교량, 도로 및 구조물의 보수공사시 긴급성이 요구되는 경우에 사용되는 것으로, 교량상판의 보수와 같은 긴급성이 필요한 공사에서 건설재료로서 가장 중요하게 요구되는 성질은 공사후 빠른 시간내에 실용강도인 200㎏/㎠이상의 강도를 발현하여 그 구조물이 목적하는 성능을 발휘하도록 하고자 하는 것이며, 일반적으로 시공후 2시간 내지 3시간 동안에 실용강도를 발현하는 시멘트를 의미한다.Fast-hardening cement is used when urgent needs are required for the repair of bridges, roads, and structures. The most important property of construction materials is the fast time after construction in constructions requiring emergency such as repair of bridge decks. By expressing the strength of the practical strength within 200kg / ㎠ or more to the structure to exhibit the desired performance, generally refers to cement expressing the practical strength for 2 hours to 3 hours after construction.
이와 같은 기본적으로 요구되는 조건을 만족시키기 위한 방법으로 수경성 화합물인 애트링자이트의 급격한 형성 및 성장을 유도하며, 타설후 2시간 내지 3시간사이에 실용강도의 발현을 목적으로 하나, 매우 빠른 응결로 인하여 작업성의 저하를 가져오는 문제가 있어 응결지연제를 혼합하여 사용하고 있다.In order to satisfy these basic requirements, it induces the rapid formation and growth of atlingite, a hydraulic compound, and aims at the development of practical strength within 2 to 3 hours after casting, but very fast condensation Due to this, there is a problem of deterioration of workability, and a condensation delaying agent is mixed and used.
긴급이 요구되는 보수공사에서 조기 실용강도의 발현을 위하여 대한민국 특허공보 공고번호 제97-8685호에서는 칼슘알루미노 설페이트, 디칼슘 실리케이트, 칼슘 알루미노 페라이트 및 결합되지 않은 칼슘 설페이트를 함유하는 클린커와 난용성 무수석고, 소석회, 지방산, 옥시카본산, 질소 함유 칼슘염 등을 함유하는 속경성 고강도 시멘트 조성물을 사용하는 기술이 알려져 있다.Korean Patent Publication No. 97-8685 discloses a clinker containing calcium aluminosulfate, dicalcium silicate, calcium alumino ferrite and unbound calcium sulfate in order to develop early practical strength in an urgently required repair work. Techniques for using a fast-hardening high strength cement composition containing poorly soluble anhydrous gypsum, hydrated lime, fatty acids, oxycarboxylic acids, nitrogen-containing calcium salts and the like are known.
그러나, 상기와 같은 속경성을 갖는 클린커를 사용하여 제조한 기존의 초속경시멘트는 수화광물인 애트링자이트(3CaOㆍAl2O3ㆍ3CaSO4ㆍ32H2O)의 결정 전이에 따라 장기강도가 저하되거나, 강도의 발현율이 낮아지는 특성을 나타내어 장기강도의 안정성이 요구되는 경우에는 구조물의 재료로서 사용상 한계를 지니고 있다.However, conventional cemented carbide cements prepared using the above fast-acting clinker have a long-term effect upon crystal transition of hydrated atringite (3CaO.Al 2 O 3 .3CaSO 4 .32H 2 O). When the strength is lowered or the expression rate of the strength is lowered and stability of long-term strength is required, it has a limitation in use as a material for the structure.
한편, 초속경시멘트를 제조하기 위하여 기존에 사용되는 클린커는 2가지의 광물계로 대별되며, 그중 하나인 칼슘플루오르알루미네이트(11CaOㆍ7Al2O3ㆍCaF2)와 칼슘실리케이트계(3CaOㆍSiO2)는 로터리 킬른에서 약 1,500℃로 소성되어 제조되는 것으로 강도발현이 안정적이고 장기적으로도 우수한 강도특성을 보이고 있으나, 소성시 고알루미나의 조성과 칼슘플루오라이드(CaF2)가 함유되어 있어 용융상이 일정이상으로 존재하게 되는 경우 조업의 안정이 어려우며 소성과정에서 불소가스의 휘발에 의한 문제가 발생할 수 있으며, 경화체내에 과량의 수산화칼슘(Ca(OH)2)이 존재하게 되어 장기적으로 안정적인 고강도 발현에 한계가 있다.On the other hand, the conventional clinker used to manufacture cemented carbide is divided into two types of minerals, one of which is calcium fluoroaluminate (11CaO · 7Al 2 O 3 · CaF 2 ) and calcium silicate (3CaO · SiO). 2 ) is produced by firing at about 1,500 ℃ in a rotary kiln, which shows stable strength and excellent strength in the long term.However, when calcined, it contains high alumina composition and calcium fluoride (CaF 2 ). If it exists above a certain level, it is difficult to stabilize the operation and a problem may occur due to the volatilization of fluorine gas in the firing process, and excessive calcium hydroxide (Ca (OH) 2 ) is present in the hardened body for stable high-strength expression in the long term. There is a limit.
또다른 계통으로는 칼슘알루미네이트(12CaOㆍ7Al2O3, CaOㆍAl2O3)계가 있으며, 이들 칼슘알루미네이트계는 전기용융로를 사용하여 1,600℃이상의 온도에서 비정질상태로 제조되고, 전기로에서의 조업기술의 확보가 요구되고, 제조단가가 높고 물성제어가 어려우며, 중요 수화광물인 애트링자이트(3CaOㆍAl2O3ㆍ3CaSO4ㆍ32H2O)의 결정 전이로 인하여 장기강도의 안정성이 떨어지는 문제가 있었다.Another system to have been manufactured from calcium temperature aluminate (12CaO and 7Al 2 O 3, CaO and Al 2 O 3) boundaries, and these calcium aluminate-based using the electric furnace over 1,600 ℃ to the amorphous state, in an electric furnace Stability of long-term strength due to high operating cost, high control of physical properties, difficult control of physical properties, and crystal transition of atringite (3CaO, Al 2 O 3, 3CaSO 4, 32H 2 O) There was a problem falling.
이와 같은 종류의 클린커를 사용하여 제조된 초속경시멘트는 높은 알루미나성분 또는 클린커와 무수석고의 반응에 의한 빠른 애트링자이트 생성반응에 초점을 맞추어 3시간이내에 실용강도의 확보를 통한 긴급보수공사에 유효하도록 설계되어 있으므로 장기적으로 안정적인 강도발현이 요구되는 구조재료로서는 사용범위에 한계가 있으며, 대부분의 초속경 시멘트로 제조한 공시체의 압축강도는 7일을 정점으로 저하되거나, 더이상 증가하지 못하는 특성을 보이고 있다.The super fast cement produced using this kind of clinker focuses on the rapid atlingite formation reaction by the reaction of high alumina or clinker and anhydrous gypsum. As it is designed to be effective in construction, there is a limit to the range of use as a structural material that requires stable strength expression in the long term, and the compressive strength of most specimens made of cemented carbide is lowered to the peak of 7 days or cannot increase any more. It is showing characteristics.
이에 본 발명자들은 초속경성 및 고강도성의 효과를 내는 주 공급원으로 아윈계 클린커와 무수석고 및 소석회를 사용하고, 후기강도를 위해 포틀랜드 시멘트를 사용하여 상술한 문제점을 해결할 수 있었고, 이에 기초하여 본 발명을 완성하였다.Therefore, the inventors of the present invention have been able to solve the above-mentioned problems by using an Arwin-based clinker, anhydrous gypsum and slaked lime as a main source of ultra-high hardness and high strength, and using Portland cement for later strength. Was completed.
따라서, 본 발명의 목적은 시공후 3시간이내에 실용강도를 나타냄과 동시에 압축강도에 있어서, 초기강도는 물론이고 후기강도에 있어서도 지속적인 강도발현 및 안정성을 유지할 수 있는 고강도의 속경성 시멘트 조성물을 제공하는데 있다.Accordingly, an object of the present invention is to provide a high-strength fast cement composition that exhibits the practical strength within 3 hours after construction and at the same time in the compressive strength, can maintain a constant strength and stability even in the initial strength as well as the later strength have.
상기 목적을 달성하기 위한 본발명의 조성물은 고강도의 속경성 시멘트 조성물에 있어서, 칼슘설포알루미네이트(3CaOㆍ3Al2O3ㆍCaSO4) 및 칼슘실리케이트(2CaO ㆍSiO2)를 주성분으로 하는 아윈계 클린커 35 내지 50중량%, 보통 포틀랜드 시멘트 25 내지 35중량%, 무수석고 10 내지 25중량%와, 소석회 5 내지 10중량%로 이루어진 혼합시멘트 100중량부에 대하여 멜라민계 고유동화제 0.1 내지 1중량부 및 응결지연제로서 구연산(Citric acid) 0.1 내지 1중량부를 포함한다.The compositions of the present invention for achieving the abovementioned objects is O as a main component a calcium sulfo aluminate (3CaO and 3Al 2 O 3 and CaSO 4) and calcium silicate (2CaO and SiO 2), in the inside hard cement composition of high strength wingye 0.1 to 1 weight of melamine-based high softening agent based on 100 parts by weight of a mixed cement comprising 35 to 50% by weight of clinker, usually 25 to 35% by weight of Portland cement, 10 to 25% by weight of anhydrous gypsum and 5 to 10% by weight of hydrated lime. And 0.1 to 1 parts by weight of citric acid as part and coagulation retardant.
이하 본 발명을 좀 더 구체적으로 살펴보면 다음과 같다.Looking at the present invention in more detail as follows.
본 발명에 따르면, 초속경 클린커로서 비교적 낮은 소성온도인 1,250∼1,350℃에서 소성이 가능하고, 비교적 제조원가가 낮은 칼슘설포알루미네이트(3CaOㆍ 3Al2O3ㆍCaSO4) 및 칼슘실리케이트(2CaOㆍSiO2)를 주성분으로 하고, 5,000㎤/g 내지 6,000㎤/g의 분말도를 갖는 아윈계 클린커를 사용한다.According to the present invention, it is possible to bake at a relatively low firing temperature of 1,250 to 1,350 ° C. as a superhard diameter clinker, and to produce calcium sulfoaluminate (3CaO · 3Al 2 O 3 · CaSO 4 ) and calcium silicate (2CaO. composed mainly of SiO 2), and uses the O wingye clinker having a fineness of 5,000㎤ / g to 6,000㎤ / g.
상기 아윈계 클린커는 시멘트의 수화물인 Ca(OH)2, 소석회 및 석고의 SO3와 반응하여 팽창성, 속경성, 조강성 등의 특성을 발휘하여 콘크리트 구조물의 수축균열방지, 케미컬 프리스트레스 콘크리트 부재, 무수축 그라우트재 등 그 응용범위가 상당히 넓은 재료이다.The Arwin-based clincher reacts with Ca (OH) 2 , which is a hydrate of cement, and SO 3 of slaked lime and gypsum, and exhibits properties such as expandability, fast hardness, and roughness to prevent shrinkage cracking of concrete structures, chemical prestressed concrete members, It is a material with a very wide application range such as a non-shrink grout material.
본 발명에서 아윈계 클린커를 35 내지 50중량로 사용하는데, 35중량미만으로 첨가되는 경우에는 아윈계 클린커에 비하여 무수석고의 양이 상대적으로 많아짐으로써 속경성에 문제가 발생하며, 50중량를 초과하면 상대적으로 속경성은 좋아지나, 보통 포틀랜드 시멘트량에 비하여 속경성 클린커의 량이 과다해짐으로써 후기강도의 발현에 문제가 발생하게 된다.In the present invention, 35 to 50 weights of Irwin-based clinker is used, but when it is added less than 35 weight, the amount of anhydrous gypsum is relatively higher than that of the Ayn-based clinker, causing problems in fast hardening, and exceeding 50 weight. If the fast hardening is relatively good, but the amount of fast hardening clinker is excessively large compared to the amount of Portland cement, there is a problem in developing late strength.
후기강도의 발현을 위해 첨가되는 보통 포틀랜드 시멘트는 25중량내지 35중량로 첨가되며, 25중량미만으로 첨가되는 경우에는 후기강도의 발현에 문제가 발생하게 되며, 35중량를 초과하면 초기강도의 발현에 문제가 발생하게 되는 것이다.Portland cement, which is added for the development of late strength, is added in an amount of 25 to 35 weights, and when it is added less than 25 weights, a problem arises in the development of late strength. Will occur.
포틀랜드 시멘트의 주요광물은 C3S, C2S, C3A 그리고 C4AF이며, 물과 접촉하면 다량의 Ca2+이온이 용액중으로 용출하여 PH값이 12정도 되는 강알칼리성을 띄게 된다. 아윈계 클린커는 C3A3, CaSO4와 C2S가 주요 광물로서, 무수석고 (CaSO4)와 물의 존재하에 결합하여 초속경 시멘트의 주요 수화광물인 애트링자이트(C3A·3CaSO4·32H2O)를 형성하는데, 이때 외부로부터 Ca2+이온을 공급하면 애트링자이트의 형성속도가 빨라져 보다 빠른 응결경화과정을 거치게 된다. 하지만 최종적으로 시멘트 경화체 내에 남는 Ca2+이온은 Ca(OH)2형태로 존재하게 되고, 다량의 Ca(OH)2는 장기적으로 경화체의 강도저하 내지는 강도발현에 나쁜 영향을 미치게 하는 원인이 된다.The main minerals in Portland cement are C 3 S, C 2 S, C 3 A and C 4 AF. When contacted with water, a large amount of Ca 2+ ions elute into the solution, resulting in strong alkalinity with a pH of about 12. In the case of the Arwin-based clinker, C 3 A 3 , CaSO 4 and C 2 S are the main minerals, and are combined in the presence of anhydrous gypsum (CaSO 4 ) and water, and the atlingite (C 3 A. 3CaSO 4 · 32H 2 O) is formed. At this time, when Ca 2+ ions are supplied from the outside, the formation rate of the atlingite is accelerated, which leads to a faster setting and curing process. But finally Ca 2+ ions remain in the cement cured body is caused to be present in the Ca (OH) 2 type, exercise a negative influence on the large amount of Ca (OH) 2 is the long term strength-naejineun reduction in strength of a cured product.
그러나 수화초기의 Ca2+이온의 과량공급으로 인해 존재하는 과잉의 Ca(OH)2를 Si4+이온과 결합시켜 C-S-H 겔(gel)을 형성시키면 장기적으로 강도가 안정되고 강도의 증가를 가져오는 효과를 얻을 수 있다.However, when excess Ca (OH) 2 is combined with Si 4+ ions to form a CSH gel due to the excessive supply of Ca 2+ ions in the early stage of hydration, the strength is stabilized and the strength is increased in the long term. The effect can be obtained.
따라서, 본 발명은 수화초기에는 급격한 애트링자이트의 형성을 위하여 소석회(Ca(OH)2) 뿐만 아니라, 보통 포틀랜드시멘트에서 용출되는 Ca2+이온을 C3A3·CaSO4및 무수석고(CaSO4)와 결합시키고 장기적으로는 보통 포틀랜드 시멘트에서 공급되는 Si4+이온에 의해 Ca(OH)2를 장기적으로 안정된 수화물인 C-S-H 겔(gel)로의 유도를 통하여 초속경성, 초기강도 증진 및 장기강도 안정성을 기하였다.Therefore, the present invention is not only hydrated lime (Ca (OH) 2 ), but also Ca 2+ ions eluted in the portland cement, such as C 3 A 3 · CaSO 4 and anhydrous gypsum in the early hydration Ultra-fast stiffness, initial strength enhancement and long-term strength through induction of Ca (OH) 2 into CSH gel, which is a long-term stable hydrate, by binding to CaSO 4 ) and in the long term by Si 4+ ions normally supplied from Portland cement. Stability was attained.
한편, 무수석고는 수화광물인 애트링자이트의 형성용으로 첨가되는 것으로, 그 사용량은 10 내지 25중량가 바람직한데, 10중량미만으로 첨가되는 경우에는 수화물의 생성이 충분하지 못하여 애트링자이트가 모노설페이트로 전이되어 강도저하의 문제를 발생하게 되고, 25중량를 초과하면 아윈계 클린커의 수화가 지연되어작업시간의 증가 및 초기강도의 발현에 지장을 초래하고 경화체의 과팽창으로 강도저하가 일어나게 된다.On the other hand, anhydrous gypsum is added for the formation of hydrated mineral atlingite, the amount of which is preferably 10 to 25 weight, when less than 10 wt. Transition to monosulfate causes a problem of strength deterioration, and when it exceeds 25 weight, the hydration of the Arwin-based clunker is delayed, which causes an increase in working time and the development of initial strength, and causes a decrease in strength due to overexpansion of the hardened body. do.
본 발명에서는 경제적 및 폐자원 활용측면에서 인산염 공업에서의 부산물로 발생하는 인산부생 무수석고를 사용하는 것이 바람직하다.In the present invention, it is preferable to use an phosphate by-product gypsum produced as a by-product of the phosphate industry in terms of economic and waste resource utilization.
상기 소석회(Ca(OH)2)는 초기강도를 향상시킬 목적으로 첨가되는 것으로, 5 내지 10중량로 사용되며, 5중량미만으로 첨가되는 경우에는 초기강도의 발현에 문제가 발생하게 되고, 10중량를 초과하면 플로우값이 급격하게 떨어지고 경화체내에 과량의 Ca(OH)2의 함량때문에 장기적으로 구조가 취약해지는 문제가 발생하게 되는 것이다.The calcined lime (Ca (OH) 2 ) is added for the purpose of improving the initial strength, it is used in 5 to 10 weight, when added in less than 5 weight will cause problems in the expression of the initial strength, 10 weight If exceeded, the flow value drops drastically and the structure becomes weak in the long term due to the excessive content of Ca (OH) 2 in the cured product.
아울러, 본 발명의 조성물은 상기 아윈계 클린커, 보통 포틀랜드 시멘트, 무수석고 및 소석회로 이루어진 혼합시멘트 100중량부에 대하여 멜라민계 고유동화제 0.1 내지 1중량부와 응결지연제로서 구연산 0.1 내지 1중량부를 포함한다.In addition, the composition of the present invention is 0.1 to 1 part by weight of melamine-based high softening agent and 0.1 to 1 weight of citric acid as a coagulant retardant based on 100 parts by weight of the mixed cement consisting of the above-mentioned winch-based clincher, ordinary portland cement, anhydrous gypsum and calcination. Contains wealth.
상기 유동화제는 많이 첨가한다고 하여 작업성의 향상에 도움이 되는 것이 아니며, 오히려 강도저하의 문제를 발생할 수 있게 되므로 통상적으로 상기 양의 범위가 바람직하고, 응결지연제로 첨가되는 구연산은 작업시의 외기온도, 습도 등의 작업환경에 따라 조절이 요구되는 것이나, 일반적으로 0.1 내지 1중량부의 범위내에서 첨가하는 것이 바람직하다.The addition of the fluidizing agent does not help to improve the workability by adding a lot, but rather, it may cause a problem of decrease in strength. Therefore, the amount is generally in the range, and citric acid added as a condensation delaying agent is the outside air temperature during operation. Although adjustment is required according to the working environment, such as humidity, it is generally preferable to add in 0.1-1 weight part.
이와 같이, 본 발명에서는 초속경성 및 고강도성의 효과를 내는 공급원으로 아윈계 클린커를 사용하고, 무수석고, 소석회 및 다량의 포틀랜드 시멘트와 혼합한후, 유동화제와 구연산을 첨가함으로써 소정의 작업시간을 확보하면서, 무수축성, 초속경성 및 우수한 장기강도 발현 및 안정성을 갖는 초속경성 고강도 시멘트를 제조하여 기존의 초속경성 시멘트보다 비교적 저렴한 비용으로 우수한 물성을 갖는 초속경 고강도 시멘트의 제조가 가능하다.As described above, in the present invention, a predetermined working time can be achieved by using an Arwin-based clinker as a source having an ultra-high hardness and high strength effect, mixing it with anhydrous gypsum, slaked lime and a large amount of portland cement, and adding a fluidizing agent and citric acid. While securing, it is possible to manufacture ultra-high strength cement having excellent physical properties at a relatively low cost than the ultra-high hardness cement by producing super-fast-hard high-strength cement having no shrinkage, ultra-high hardness and excellent long-term strength expression and stability.
이하, 실시예를 통하여 본 발명을 좀 더 구체적으로 살펴보지만, 하기 예에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.
실시예 1 내지 2Examples 1-2
클린커 광물로서 칼슘설포알루미네이트(3CaOㆍ3Al2O3ㆍCaSO4) 및 칼슘실리케이트(2CaOㆍSiO2)를 주성분으로 하고, 분말도가 5,500㎤/g인 아윈계 클린커, 인산염공업에서의 부산물인 무수석고, 공업용으로 제조된 소석회, 한라사 보통 포틀랜드 시멘트, 멜라민계 유동화제(독일 SKW사, 상품명 Melment F4000) 및 구연산을 하기 표 1에 나타나 있는 바와 같은 조성으로 혼합하여 50×50×50mm의 초속경성 시멘트 공시체를 제조하고, 플로우 특성 및 압축강도를 하기 표 1에 함께 나타내었다.As a clinker mineral, it is calcium sulfoaluminate (3CaO.3Al 2 O 3 .CaSO 4 ) and calcium silicate (2CaO.SiO 2 ) as main components. By-product anhydrous gypsum, industrially manufactured slaked lime, Halla's ordinary portland cement, melamine-based fluidizing agent (SKW, Germany, Melment F4000) and citric acid were mixed in a composition as shown in Table 1 below 50 × 50 × 50 mm The super fast cement specimen was prepared, and the flow characteristics and the compressive strength are shown together in Table 1 below.
비교예 1 내지 3Comparative Examples 1 to 3
비교예 1은 미국 U사의 초속경성 시멘트이고, 비교예 2는 국내 S사의 초속경성 시멘트이며, 비교예 3은 국내 U사의 초속경성 시멘트이다.Comparative Example 1 is an ultra fast cement of U company, Comparative Example 2 is an ultra fast cement of S company in Korea, and Comparative Example 3 is an ultra fast cement of U company in Korea.
1) 및 2)는 시멘트 100중량부에 대한 사용량1) and 2) are used amount of 100 parts by weight of cement
3)은 KSL 5111(1987) 방법으로 측정3) measured by KSL 5111 (1987) method
4)는 KSL 5105 방법으로 측정4) Measured by KSL 5105 method
상기 표 1로부터 알 수 있는 바와 같이, 본 발명의 조성에 의하여 제조된 속경성 시멘트는 비교예의 경우와 비교할 때 전반적으로 압축강도 플로우 특성등이 우수하며, 2시간 경화후의 압축강도가 약 240㎏/㎤이상, 7일 강도가 약 500㎏/㎤이상, 28일 강도가 약 600㎏/㎤이상을 나타내고 있으며, 초기강도 및 후기강도에 있어서도 우수한 압축강도를 나타내고 있어, 본 발명에서 목적으로 하는 효과를 가져옴으로써 시급성을 요구하는 구조물의 보수에 유용하게 사용될 수 있다.As can be seen from Table 1, the fast-hard cement prepared by the composition of the present invention is excellent in overall compressive strength flow characteristics and the like compared to the case of the comparative example, the compressive strength after curing for 2 hours about 240 kg / It exhibits more than 3 cm 3, 7 days strength of about 500 kg / cm 3 and 28 days strength of about 600 kg / cm 3, and shows excellent compressive strength even in initial strength and late strength. It can be usefully used for repairing structures requiring urgency.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030093632A (en) * | 2002-06-04 | 2003-12-11 | 홍정희 | Mixed cement, mortar or concrete, and manufacturing method thereof |
| KR100880930B1 (en) * | 2008-07-22 | 2009-02-04 | 최이현 | Cement composition for rapid hardening |
| KR100880932B1 (en) | 2008-07-22 | 2009-02-04 | 최이현 | Producing method for ultra rapid hardening polymer modified concrete |
| KR100894081B1 (en) | 2008-11-26 | 2009-04-21 | 송이콘주식회사 | Concrete composition having water permeability utilizing scoria and concrete structure utilizing the composition |
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1999
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| KR20030093632A (en) * | 2002-06-04 | 2003-12-11 | 홍정희 | Mixed cement, mortar or concrete, and manufacturing method thereof |
| KR100880930B1 (en) * | 2008-07-22 | 2009-02-04 | 최이현 | Cement composition for rapid hardening |
| KR100880932B1 (en) | 2008-07-22 | 2009-02-04 | 최이현 | Producing method for ultra rapid hardening polymer modified concrete |
| KR100938884B1 (en) | 2008-10-29 | 2010-01-27 | 한국광해관리공단 | Accelerating mortar for grouting underground cavity by using a eco-friendly cement mineral kingdom and grouting method using this |
| KR100894081B1 (en) | 2008-11-26 | 2009-04-21 | 송이콘주식회사 | Concrete composition having water permeability utilizing scoria and concrete structure utilizing the composition |
| KR100979180B1 (en) | 2009-07-31 | 2010-09-02 | 쌍용양회공업(주) | Composition of rapid setting micro cement |
| US10065892B2 (en) | 2012-07-25 | 2018-09-04 | Jin-Man Kim | Hydraulic binder composition using rapidly-cooled steelmaking reduced slag powder, and method of preparing the same |
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