KR100306227B1 - Compounding composition for cement having high hardness - Google Patents
Compounding composition for cement having high hardness Download PDFInfo
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- KR100306227B1 KR100306227B1 KR1019990017274A KR19990017274A KR100306227B1 KR 100306227 B1 KR100306227 B1 KR 100306227B1 KR 1019990017274 A KR1019990017274 A KR 1019990017274A KR 19990017274 A KR19990017274 A KR 19990017274A KR 100306227 B1 KR100306227 B1 KR 100306227B1
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- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 239000004568 cement Substances 0.000 title claims abstract description 23
- 238000013329 compounding Methods 0.000 title 1
- 239000006227 byproduct Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 108010001779 Ancrod Proteins 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 239000002956 ash Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 21
- 239000004567 concrete Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 10
- 239000000047 product Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002440 industrial waste Substances 0.000 abstract description 5
- 239000011449 brick Substances 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000011372 high-strength concrete Substances 0.000 abstract description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 abstract 1
- 229910052602 gypsum Inorganic materials 0.000 description 7
- 239000010440 gypsum Substances 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910021487 silica fume Inorganic materials 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 239000011398 Portland cement Substances 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910001341 Crude steel Inorganic materials 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000011083 cement mortar Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- PGZIKUPSQINGKT-UHFFFAOYSA-N dialuminum;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O PGZIKUPSQINGKT-UHFFFAOYSA-N 0.000 description 1
- 239000011381 foam concrete Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- -1 ordinary Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011513 prestressed concrete Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/0445—Synthetic gypsum, e.g. phosphogypsum
-
- 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
- C04B18/18—Waste materials; Refuse organic
- C04B18/24—Vegetable refuse, e.g. rice husks, maize-ear refuse; Cellulosic materials, e.g. paper, cork
- C04B18/241—Paper, e.g. waste paper; Paper pulp
- C04B18/243—Waste from paper processing or recycling paper, e.g. de-inking sludge
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/0088—Compounds chosen for their latent hydraulic characteristics, e.g. pozzuolanes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/0091—Organic co-binders for mineral binder compositions
- C04B2103/0092—Organic co-binders for mineral binder compositions for improving green strength
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
본 발명은 콘크리트 파일, 콘크리트폴, 고강도 콘크리트 벽돌·블럭 및 고강도의 프리캐스트 제품의 주성분인 시멘트에 첨가하는 혼화재 조성물에 관한 것으로, 좀 더 상세하게는 고강도 시멘트용 혼화재 조성물에 있어서, Ⅱ형 무수석고 분말 70∼90중량%, 아윈계 클린커 1∼10중량% 및 입도분리된 제지 애쉬 5∼20중량%로 구성된 고강도 시멘트용 혼화재 조성물에 관한 것이다. 본 발명에 따른 조성물은 제지산업에서 발생되는 산업 폐부산물인 제지 애쉬를 입도분리하여 새로운 포졸란 물질로 이용함으로써 제조비 절감 및 환경오염 방지에 큰 역할을 하면서 상압 증기 양생으로 고강도를 발휘할 수 있는 효과가 있다.The present invention relates to admixture compositions added to concrete piles, concrete poles, high-strength concrete bricks / blocks, and cements, which are the main components of high-strength precast products. It is related with the admixture composition for high-strength cement which consists of 70 to 90 weight% of powders, 1 to 10 weight% of Irwin type | system | group clinders, and 5 to 20 weight% of the papermaking ashes which were separated from the particle size. The composition according to the present invention has the effect of exerting high strength with atmospheric steam curing while playing a major role in reducing manufacturing costs and preventing environmental pollution by separating the paper ash, which is an industrial waste by-product generated in the paper industry, as a new pozzolanic material. .
Description
본 발명은 콘크리트 파일, 콘크리트폴, 고강도 콘크리트 벽돌·블록 및 고강도의 프리캐스트 제품의 주성분인 시멘트에 첨가하는 혼화재 조성물에 관한 것으로, 좀 더 상세하게는 시멘트에 단순 첨가함으로써 고온 및 고압 증기양생이 아닌 상압 증기 양생만으로도 고강도를 발휘할 뿐만 아니라, 제조비용 절감과 산업 폐부산물의 활용에 의해 환경친화적인 고강도 시멘트용 혼화재 조성물에 관한 것이다.The present invention relates to admixture compositions added to concrete piles, concrete poles, high-strength concrete bricks and blocks, and cements, which are the main components of high-strength precast products. The present invention relates to an admixture composition for high-strength cement that is environmentally friendly by not only exerting high strength with atmospheric steam curing but also reducing manufacturing cost and utilizing industrial waste by-products.
일반적으로, 시멘트 모르타르나 콘크리트 2차제품을 고강도화시키기 위해서는 보통 포틀랜드 시멘트 단독 또는 실리카 물질을 혼합하여 고온 및 고압에서 증기 양생을 하거나, 무수석고계 고강도 혼화재를 시멘트에 혼합하여 상압 증기 양생시켜 고강도화를 이루고 있다. 상압 증기 양생용 고강도 혼화재는 주로 무수석고를 주성분으로 하고, 실리카 흄, 슬래그 분말, 플라이 애쉬, 규조토 및/또는 카올린 분말 등의 포졸란성 물질을 혼합하여 제조하고 있다.In general, in order to increase the strength of cement mortar or concrete secondary products, steam curing is usually performed by mixing only Portland cement alone or silica material at high temperature and high pressure, or by mixing the anhydrous gypsum-based high strength admixture with cement to atmospheric pressure steam curing to achieve high strength. have. The high-strength admixture for atmospheric vapor curing is mainly manufactured by mixing anhydrous gypsum with pozzolanic substances such as silica fume, slag powder, fly ash, diatomaceous earth and / or kaolin powder.
상압 증기 양생에 따른 수화생성물의 생성시기 및 형태를 조절하여 고강도화를 이루기 위해서는 무수석고는 분쇄하여 미세분말을 사용하고, 포졸란 물질로는 반응성이 우수한 실리카 흄이나 미분쇄된 슬래그를 주로 사용하고 있다.In order to achieve high strength by controlling the formation time and shape of the hydrated product according to atmospheric steam curing, anhydrous gypsum is pulverized and fine powder is used. As the pozzolanic material, silica fume or finely ground slag having high reactivity is mainly used.
상기 용어 '포졸란 물질'이란 콘크리트 혼합재의 일종으로서 그 자체는 수경성을 지니고 있지 아니하나, 콘크리트층의 물에 용해되어 있는 산화칼슘과 상온에서 서서히 반응하여 불용성의 화합물을 형성할 수 있는 실리카 물질을 포함하고 있는 미분상태의 재료로서 규산칼슘 수화물을 형성시키는 작용을 하는 물질을 의미한다.The term 'pozzolanic material' is a kind of concrete mixture, which itself does not have hydraulic properties, but includes a silica material which can slowly react at room temperature with calcium oxide dissolved in water of the concrete layer to form an insoluble compound. It means the substance which acts to form calcium silicate hydrate as a finely divided material.
한편, 종래 무수석고계 혼화재의 고강도 발현기구는 무수석고의 첨가에 의해 C3S의 가수분해가 향상되어 Ca(OH)2의 생성이 촉진되고, 시멘트중의 C3A와의 반응이 활성화되어 증기양생이 개시되면서 생성되는 침상결정의 수화물인 애트링자이트가 다량의 자유수를 고정시켜 상대적으로 물시멘트의 비를 낮추고 큰 공극을 충진하여 조직을 치밀화시키며, 또한 플라이 애쉬, 실리카 흄, 슬래그, 규조토, 카올린계 물질 등의 포졸란 물질을 혼합하여 불용성의 수화생성물인 CSH 겔의 생성이 증대되기 때문이다.On the other hand, the high-strength expression mechanism of the conventional anhydrous gypsum-based admixture improves the hydrolysis of C 3 S by the addition of anhydrous gypsum to promote the production of Ca (OH) 2 , and the reaction with C 3 A in the cement is activated to steam Atlingite, a hydrate of acicular crystals produced by curing starts, fixes a large amount of free water, lowers the ratio of water cement and fills large voids, densifying tissue, and also makes fly ash, silica fume, slag, This is because the production of CSH gel, which is an insoluble hydration product, is increased by mixing pozzolanic substances such as diatomaceous earth and kaolin-based substances.
이와 같이, 무수석고와 C3A와의 반응에 의해 애트링자이트가 생성되는데, 증기양생이 개시되면서 집중적으로 형성되도록 그 생성시기 및 형태를 조절하기 위해서 대한민국 공개특허공보 공개번호 제96-037607호에서는 평균입도가 1∼15㎛인 Ⅱ형 무수석고 및 평균입도가 15∼50㎛인 Ⅱ형 무수석고를 함께 사용하여 시멘트의 압축강도를 다소 향상시켰으나 만족할만한 수준은 못되며, 또한 무수석고의 미분쇄에 따른 별도의 공정 및 비용이 발생하는 단점이 있다.As such, the atlingite is produced by the reaction of anhydrous gypsum and C 3 A, in order to control the production time and form so as to form intensively as the steam curing starts, Korean Laid-Open Patent Publication No. 96-037607 Has improved the compressive strength of cement somewhat by using Ⅱ anhydrous gypsum with an average particle size of 1 to 15㎛ and Ⅱ anhydrous gypsum with an average particle size of 15 to 50㎛, but it is not satisfactory. There are disadvantages in that separate processes and costs are caused by grinding.
아울러, 불용성의 수화생성물을 생성시켜 증기양생후 강도 발현이 빨리 이루어지도록 첨가되는 포졸란 물질로서, 대표적으로 것으로는 실리카 흄, 고로 슬래그 등이 있으나, 실리카 흄의 경우는 반응성은 뛰어나지만 국내에서 거의 생산되지 않는 고가의 물질로서, 그 기능에 비하여 제조원가의 상승에 미치는 영향이 커서 사용이 기피되고 있으며, 고로 슬래그의 경우는 별도의 분쇄공정이 요구되고, 그 사용량이 많을수록 콘크리트의 중성화를 촉진하여 철근부식등에 의한 장기적인 내구성에 문제가 있게 된다.In addition, the pozzolanic material is added to generate an insoluble hydration product so that the strength is quickly developed after steam curing, and typical examples include silica fume and blast furnace slag, but silica fume is highly reactive but almost produced in Korea. It is an expensive material that is not expensive, and its use is avoided because it has a greater effect on the increase in manufacturing cost compared to its function. In the case of blast furnace slag, a separate grinding process is required. There is a problem in long-term durability due to the back.
또한, 플라이 애쉬는 품질 편차가 크고, 카올린계 물질은 반응성을 갖도록 열처리를 하여야 하는 등의 단점이 있어 결국 제품의 제조비용의 상승을 초래하는 단점이 있다. 따라서, 가격이 저렴하면서 높은 포졸란 효과를 가져올 수 있는 대체물질의 개발이 요구되어 왔다.In addition, the fly ash has a disadvantage in that the quality variation is large, the kaolin-based material has to be heat-treated to have a reactivity, resulting in an increase in the manufacturing cost of the product. Therefore, there is a need for the development of alternative materials that can bring a high pozzolanic effect at a low price.
한편, 대한민국 공개특허공보 공개번호 제96-7496호에서는 제지슬러지 소각회(이하 '제지 애쉬'라고도 함)를 경량 기포 콘크리트의 제조에 첨가한 바 있으나,포졸란 물질로의 사용은 아니다.Meanwhile, Korean Laid-Open Patent Publication No. 96-7496 has added paper sludge incineration ash (hereinafter referred to as 'paper ash') in the manufacture of lightweight foam concrete, but it is not used as a pozzolanic material.
일반적인 제지슬러지 소각회는 그 물성 및 성분이 하기 표 1과 같으며, 도 1의 그래프에서 알 수 있는 바와 같이 함유되어 있는 성분중 미반응성의 실리카 결정성분이 다량 함유되어 있어 포졸란 물질로서의 기능을 제대로 발휘하지 못하는 문제가 있었다.In general, the paper sludge incineration ash has the physical properties and components as shown in Table 1 below, and as shown in the graph of FIG. There was a problem that could not be exercised.
이에 본 발명에서는 상술한 문제점에 착안하여 반응성을 촉진시키기 위한 재료로써 무수석고를 분쇄하는 대신 칼슘설포알루미네이트(3CaO·3Al2O3·CaSO4)가 주광물인 아윈계 클린커를 사용하고, 포졸란 물질로 적합하지 못하였던 제지 애쉬를 전처리하여 사용하면 상술한 문제점을 해결할 수 있음을 발견하였고, 본 발명은 이에 기초하여 완성되었다.Therefore, in the present invention, instead of pulverizing anhydrous gypsum as a material for promoting the reactivity in view of the above-mentioned problems, using an anneal-based clincher whose calcium sulfoaluminate (3CaO · 3Al 2 O 3 · CaSO 4 ) is the main mineral, It has been found that the above-mentioned problems can be solved by using a paper ash that is not suitable as a pozzolanic material, and the present invention has been completed based on this.
따라서, 본 발명의 목적은 시멘트에 단순 첨가함으로써 고온 및 고압 증기양생이 아닌 상압 증기 양생만으로도 고강도를 발휘할 뿐만 아니라, 제조비용 절감과 산업 폐부산물의 활용에 의해 환경친화적인 고강도 시멘트용 혼화재 조성물을 제공하는데 있다.Accordingly, an object of the present invention is to provide a high-strength cement admixture composition that is environmentally friendly by not only high temperature and high pressure steam curing but also normal pressure steam curing by simply adding to cement, and reducing manufacturing costs and utilizing industrial waste byproducts. It is.
도 1은 일반적인 제지슬러지 소각회의 X-선 회절분석그래프이고,1 is an X-ray diffraction graph of a typical paper sludge incineration ash,
도 2는 본 발명에 따라 입도 분리후의 제지슬러지 소각회의 X-선 회절분석 그래프로서, ●는 SiO2(석영)이고, ▲는 Mg8Si4O10(OH)2이며, ◆는 (Na·K)(Si3Al)O8이다.FIG. 2 is an X-ray diffraction graph of paper sludge incineration ash after particle size separation according to the present invention, wherein ● is SiO 2 (quartz), ▲ is Mg 8 Si 4 O 10 (OH) 2 , and ◆ is (Na · K) (Si 3 Al) O 8 .
상기 목적을 달성하기 위한 본 발명의 조성물은 고강도 시멘트용 혼화재 조성물에 있어서, Ⅱ형 무수석고 분말 70∼90중량, 아윈계 클린커 1∼10중량및 입도분리된 제지 애쉬 5∼20중량로 구성된다.The composition of the present invention for achieving the above object is composed of 70 to 90 weight of type II anhydrous gypsum powder, 1 to 10 weight of Arwin-based clinker and 5 to 20 weight of separated paper ash in the high-strength cement admixture composition .
이하 본 발명을 첨부된 도면을 참조하여 좀 더 구체적으로 살펴보면 다음과 같다.Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.
전술한 바와 같이, 본 발명에서 고강도 혼화재의 제조에 이용한 원료는 별도 분쇄하지 않은 평균입도가 1∼50㎛인 Ⅱ형 무수석고 분말 70∼90중량, 아윈계 클린커 1∼10중량및 입도분리된 제지 애쉬 5∼20중량로 구성된다.As described above, in the present invention, the raw material used for the preparation of the high strength admixture is 70 to 90 weight of type II anhydrous gypsum powder having an average particle size of 1 to 50 µm that is not separately pulverized, 1 to 10 weight, and particle size separated from the winch Paper ash consists of 5 to 20 weights.
한편, 시멘트중에 존재하는 칼슘알루미네이트상과 석고의 수화반응에 의해서 생성되는 결정상의 애트링자이트 수화물의 생성시기와 형태는 석고의 반응성에 따라서 결정된다.On the other hand, the generation time and form of the crystalline phase atlingite hydrate produced by the hydration reaction of calcium aluminate phase and gypsum in cement are determined according to the reactivity of the gypsum.
이에 본 발명에서는 별도의 비용발생을 없애기 위하여 분쇄하지 않은 원래상태의 무수석고(원래상태의 무수석고의 블레인(Blaine)값은 약 3,000㎠/g 정도의 분말상임)를 기본물질로 하고, 대략적으로 분쇄한 무수석고(블레인(Blaine)값은 약 13,000㎠/g 정도)와 아윈계 클린커를 사용하여 증기양생 개시전의 시멘트광물의 활성화를 극대화하고, 증기양생이 개시되면서 집중적으로 애트링자이트가 생성되도록 하여 초기강도의 상승과 내구성의 증진을 이루었다.Therefore, in the present invention, in order to eliminate any additional cost, the original material is an anhydrous gypsum (the Blaine value of the original anhydrous gypsum is about 3,000 cm 2 / g in powder form), which is not pulverized. Using crushed anhydrous gypsum (Blaine value is about 13,000cm2 / g) and an Arwin-based clunker to maximize the activation of cement minerals prior to the start of steam curing, and at the beginning of steam curing, To increase the initial strength and increase the durability.
본 발명에 사용된 무수석고는 인산염 공업에서 부산물로 생성되는 인산부생 무수석고가 자원 재활용 측면에서 바람직하며, 그 사용량은 70∼90중량%이다. 이때, 무수석고의 사용량이 70중량%미만이면 내구성이 저하되고, 90중량%를 초과하면 초기 강도값이 낮아지는 경향이 있다.Anhydrous gypsum used in the present invention is preferably a phosphate by-product anhydrous gypsum produced as a by-product from the phosphate industry in terms of resource recycling, the amount is 70 to 90% by weight. At this time, if the amount of anhydrous gypsum is less than 70% by weight, the durability is lowered, and if it exceeds 90% by weight, the initial strength value tends to be lowered.
본 발명에 사용되는 아윈계 클린커는 칼슘설포알루미네이트 및 칼슘실리케이트(C2S)가 주성분으로서, 시멘트의 수화물인 Ca(OH)2및 석고의 SO3와 반응하여 팽창성, 속경성, 조강성등의 특성을 발휘하여 콘크리트구조물의 수축균열방지, 케미컬 프리스트레스 콘크리트부재, 무수축 그라우트재등 그 응용범위가 상당히 넓은 재료이며, 또한 비교적 낮은 온도에서 생성되고 분쇄성이 양호하기 때문에 에너지절약면에서도 크게 기여할 수 있는 재료이다.Irwin-based clinker used in the present invention is calcium sulfo aluminate and calcium silicate (C 2 S) as the main component, the hydrate of Ca (OH) 2 of cement and SO 3 of gypsum reacts with expandability, fastness, roughness This material has a wide range of applications such as preventing shrinkage cracking of concrete structures, chemical prestressed concrete members, and non-shrink grouting materials. It is a material that can contribute.
상기 아윈계 클린커의 분말도는 약 4,000∼5,000㎠/g인 것이 본 발명에 바람직하며, 그 사용량은 1∼10중량%이다. 이때, 1중량%미만이면 그 첨가효과가 미미하여 애트링자이트 생성에 기여하지 못해 결국 초기강도 발현에 문제가 있고, 10중량%를 초과하면 증기양생 개시전에 이미 다량의 애트링자이트 생성으로 인해 증기양생에 의한 강도발현 및 장기적인 강도발현이 저하하고 내구성이 저하되는 경향이 있다.It is preferable in the present invention that the powder degree of the above-mentioned winker is about 4,000 to 5,000 cm 2 / g, and the amount thereof is 1 to 10% by weight. At this time, if the content is less than 1% by weight, the effect of addition is insignificant, which does not contribute to the formation of atlingite, and thus, there is a problem in the initial strength expression. There is a tendency that strength expression and long-term strength expression by steam curing are lowered and durability is lowered.
본 발명에서는 제지산업에서 발생되는 산업 폐부산물인 제지 애쉬를 5∼20중량로 사용하는데, 제지산업에서 발생된 제지 애쉬 자체는 수경성이 없으나, 시멘트에서 생성되는 Ca(OH)2와 반응하여 불용성 수화물을 생성시키는 포졸란 물질로 이용하는 것이다.In the present invention, 5 to 20 weight of paper ash, which is an industrial waste by-product generated in the paper industry, is used. However, the paper ash generated in the paper industry itself is not hydrophobic, but reacts with Ca (OH) 2 produced in cement to insoluble hydrate. It is used as a pozzolanic material to produce a.
그러나, 원래상태의 제지 애쉬는 미반응성 실리카(결정성 석영)가 함유되어 있어 포졸란 반응성이 저하되기 때문에 초기강도 발현에 문제가 있다(상기 표 1 참조). 따라서, 분리기(separator)로 입도분리하면 미반응성 실리카질의 거의 대분분이 제거되고 반응성이 뛰어난 비정질 상태가 된다.However, since the original paper ash contains unreacted silica (crystalline quartz), pozzolanic reactivity is lowered, there is a problem in initial strength expression (see Table 1 above). Therefore, when the particle size is separated by a separator, most of the unreacted silica is removed and the amorphous state is excellent in reactivity.
본 발명에 따라 입도분리된 제지 애쉬의 물성 및 성분을 하기 표 2 및 도 2에 나타내었다.Physical properties and components of the papermaking ash particle size separated according to the present invention are shown in Table 2 and FIG. 2.
상기 표 2 및 도 2와 제지 애쉬의 입도분리전의 표 1 및 도 1을 비교하면, 미반응성 SiO2인 석영성분이 거의 대부분 제거되어 비정질 물질로 이루어지고, 화학성분은 SiO2가 30∼40이고, CaO는 30∼40이며, 비표면적도가 3,000∼5,000㎠/g인 제지애쉬가 포졸란 반응성면에서 바람직한 물질임을 확인할 수 있다.A comparison of the Table 2 and Figure 2, and paper size separation in Table 1 and Figure 1, prior to the ash, non-reactive SiO 2 component is quartz is almost removed is made of amorphous material, chemical composition SiO 2 is 30 to 40 and , CaO is 30 to 40, it can be confirmed that paper ash having a specific surface area of 3,000 to 5,000 cm 2 / g is a preferred material in terms of pozzolanic reactivity.
한편, 본 발명에 사용되는 제지 애쉬의 사용량은 5∼20중량가 바람직한데, 5중량미만이면 첨가효과가 미미하고, 20중량를 초과하면 초기강도 발현이 저하되는 경향이 있다.On the other hand, the amount of paper ash used in the present invention is preferably 5 to 20 weight, but less than 5 weight, the effect of addition is insignificant, and if it exceeds 20 weight, the initial strength expression tends to be lowered.
이러한 조성을 갖는 조성물을 보통·중용열·조강·초조강 등 각종 시멘트에5∼50중량혼합하고, 60∼85℃의 온도에서 증기양생하면 애트링자이트, CSH 겔, Ca(OH)2등의 수화물이 생성되어 고강도를 발현하게 된다.A composition having such a composition is mixed with 5 to 50 weights in various cements such as ordinary, medium heat, crude steel, and crude steel, and steam cured at a temperature of 60 to 85 ° C., such as atlingite, CSH gel, and Ca (OH) 2 . Hydrates are produced, resulting in high strength.
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 the following examples, but the scope of the present invention is not limited to the following examples.
실시예 1Example 1
별도 분쇄하지 않은 인산부생 무수석고 90중량, 분말도가 약 4,500㎠/g인 아윈계 클린커 3중량및 분리기로 분리하여 상기 표 2와 같은 조성을 갖는 제지 애쉬 7중량를 혼합하였다.90 weight of phosphate by-product anhydrous gypsum, powder weight of about 4,500 cm 2 / g, and 3 weights of Awin-based clinker separated by a separator and 7 weight of paper ash having a composition as shown in Table 2.
상기 조성물 76kg과 보통 포틀랜드 시멘트 684kg을 혼합하여 760kg의 결합재를 조제하고, 강도시험용 주문진 표준사(규격: KS L 5100) 1,862kg, 혼합수량 228kg, 유동화제(Mighty 150, 일본) 76kg을 첨가하여 시멘트 몰탈을 제조하고, 압축강도(1일, 7일, 28일), 휨강도(1일, 28일), 수축율(7일, 28일)을 측정하였으며, 그 결과를 하기 표 3에 기재하였다.76 kg of the composition and 684 kg of ordinary Portland cement were mixed to prepare 760 kg of binder, and 1,862 kg of Jumunjin standard yarn (standard: KS L 5100) for strength test, 228 kg of mixed quantity, 76 kg of fluidizing agent (Mighty 150, Japan) were added to cement. Mortar was prepared, and the compressive strength (1 day, 7 days, 28 days), flexural strength (1 day, 28 days), shrinkage (7 days, 28 days) were measured, and the results are shown in Table 3 below.
실시예 2Example 2
상기 실시예 1에서 별도 분쇄하지 않은 인산부생 무수석고 60중량, 블레인이 약 13,000㎠/g인 인산부생 무수석고 25중량, 분말도가 약 4,500㎠/g인 아윈계 클린커 5중량및 분리기로 분리하여 상기 표 2와 같은 조성을 갖는 제지 애쉬 10중량를 혼합한 것을 제외하고는 동일하게 실시하였고, 그 결과를 하기 표 3에 기재하였다.In Example 1, 60 weights of phosphate by-product gypsum, which is not separately pulverized, 25 weights of by-product phosphate anhydrous gypsum having a grain of about 13,000 cm 2 / g, separated by 5 weights and separators of Arwin-based cleaner It was carried out in the same manner except for mixing 10 weight of the paper ash having a composition as shown in Table 2, the results are shown in Table 3 below.
1)은 KS L 5105 방법에 의거 측정1) Measured according to KS L 5105 method
2)는 JIS R 5201 방법에 의거 측정2) Measured according to JIS R 5201 method
3)은 KS F 2424 방법에 의거 측정3) Measured according to KS F 2424 method
4)는 보통 포틀랜드 시멘트(한라시멘트사 제품)4) is usually portland cement (manufactured by Halla Cement)
실시예 3Example 3
별도 분쇄하지 않은 인산부생 무수석고 90중량, 분말도가 약 4,500㎠/g인 아윈계 클린커 3중량및 분리기로 분리하여 상기 표 2와 같은 조성을 갖는 제지 애쉬 7중량를 혼합한 조성물 54kg과 보통 포틀랜드 시멘트 486kg을 혼합하여 540kg의 결합재를 조제하고, 물 137kg, 세골재로써 육사 615kg, 굵은 골재로써 최대크기 19mm인 쇄석 1,133kg, 및 유동화제 90kg과 함께 콘크리트용 혼합기에서 혼합한 뒤 내경 200mm, 높이 300mm인 원심몰드에 채워 원심성형한 콘크리트의 1일, 7일, 28일 압축강도를 측정하여 하기 표 4에 기재하였다.Composition 54kg and ordinary portland cement, which is 90 weight of phosphate-free anhydrite gypsum, powder weight of about 4,500 cm 2 / g, and 3 weight of Arwin-based clinker, separated by a separator, and 7 weight of paper ash having the composition shown in Table 2 above. 486kg mixed to prepare 540kg of binder, 137kg of water, 615kg of fine aggregate, 615kg of coarse aggregate, 1,133kg of crushed stone of maximum size 19mm, and 90kg of fluidizing agent, and then mixed in concrete mixer and centrifugal of 200mm in diameter and 300mm in height The compressive strength of the 1st, 7th, and 28th days of the centrifugal concrete filled in the mold was measured and listed in Table 4 below.
실시예 4Example 4
상기 실시예 3에서 별도 분쇄하지 않은 인산부생 무수석고 60중량, 블레인이약 13,000㎠/g인 인산부생 무수석고 25중량, 분말도가 약 4,500㎠/g인 아윈계 클린커 5중량및 분리기로 분리하여 상기 표 2와 같은 조성을 갖는 제지 애쉬 10중량를 혼합한 것을 제외하고는 동일하게 실시하였고, 그 결과를 하기 표 4에 기재하였다.In Example 3, 60 weights of phosphate by-product gypsum, which is not separately pulverized, 25 weights of by-product phosphate gypsum with Blaine about 13,000 cm 2 / g, separated by 5 weight and separator of Arwin-based clincher having a powder degree of about 4,500 cm 2 / g It was carried out in the same manner except for mixing 10 weight of the paper ash having a composition as shown in Table 2, the results are shown in Table 4 below.
1)은 KS F 2454 방법에 의거 측정1) Measured according to KS F 2454 method
이상에서 알 수 있는 바와 같이, 본 발명에 따른 조성물은 시멘트 몰탈에 적용되어 1일 압축강도 및 휨강도 모두 약 20% 정도 상승하였고, 28일 수축율도 비교예에 비하여 상당히 낮은 우수한 물성을 나타내었다. 또한, 본발명의 조성물을 콘크리트에 적용할 때에도 각각 약 20% 및 10% 상승한 1일 강도와 12% 및 25% 정도 상승한 28일 압축강도 값을 나타내었다.As can be seen from the above, the composition according to the present invention was applied to cement mortar, and the daily compressive strength and the flexural strength were both increased by about 20%, and the 28-day shrinkage ratio was significantly lower than that of the comparative example. In addition, when the composition of the present invention was applied to concrete, the daily strength increased by about 20% and 10% and the 28-day compressive strength value increased by 12% and 25%, respectively.
전술한 바와 같이, 본발명에 따른 혼화재 조성물은 애트링자이트의 생성시기를 조절하기 위해 무수석고를 별도로 분쇄하지 않고, 속경성 및 팽창성의 효과를 나타내는 아윈계 클린커를 사용하며, 제지산업에서 발생되는 산업폐부산물인 제지 애쉬를 입도분리하여 새로운 포졸란 물질로 이용함으로써 제조비 절감 및 환경오염 방지에 큰 역할을 하면서 상압 증기양생으로 고강도를 발휘할 수 있는 효과가 있다.As described above, the admixture composition according to the present invention does not separately grind anhydrous gypsum in order to control the production time of atlingite, and uses an Arwin-based clincher that shows the effect of rapid hardening and expansion, and in the paper industry By separating the particle size of the produced industrial waste by-products and using it as a new pozzolanic material, it plays an important role in reducing manufacturing costs and preventing environmental pollution, thereby exerting high strength with atmospheric steam curing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100454673B1 (en) * | 2001-12-03 | 2004-11-05 | 동양산전 주식회사 | Expansion production admixture |
| KR20160100424A (en) | 2015-02-13 | 2016-08-24 | 삼부건설공업 주식회사 | The composition for manufacturing pretensioned spun high strength concrete pile and method of producing the same |
| KR20160150136A (en) | 2015-06-18 | 2016-12-29 | 삼부건설공업 주식회사 | The composition for manufacturing pretensioned spun high strength concrete pile and method of producing the same |
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| KR100694899B1 (en) * | 2005-06-17 | 2007-03-13 | (주) 지오시스 | Self aged expanding and pressurizing Grout and nailing method using it |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100454673B1 (en) * | 2001-12-03 | 2004-11-05 | 동양산전 주식회사 | Expansion production admixture |
| KR20160100424A (en) | 2015-02-13 | 2016-08-24 | 삼부건설공업 주식회사 | The composition for manufacturing pretensioned spun high strength concrete pile and method of producing the same |
| KR20160150136A (en) | 2015-06-18 | 2016-12-29 | 삼부건설공업 주식회사 | The composition for manufacturing pretensioned spun high strength concrete pile and method of producing the same |
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