KR950008585B1 - Composition of cement ca-mg - Google Patents
Composition of cement ca-mg Download PDFInfo
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- KR950008585B1 KR950008585B1 KR1019920016180A KR920016180A KR950008585B1 KR 950008585 B1 KR950008585 B1 KR 950008585B1 KR 1019920016180 A KR1019920016180 A KR 1019920016180A KR 920016180 A KR920016180 A KR 920016180A KR 950008585 B1 KR950008585 B1 KR 950008585B1
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- cement
- magnesium
- magnesium oxide
- calcium
- calcium carbonate
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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
- 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
- C04B28/10—Lime cements or magnesium oxide cements
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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
- C04B9/00—Magnesium cements or similar cements
- C04B9/11—Mixtures thereof with other inorganic cementitious materials
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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
- 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
- C04B14/34—Metals, e.g. ferro-silicon
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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
- C04B2/00—Lime, magnesia or dolomite
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Abstract
Description
제1도는 본 발명의 시멘트 조성물과 각 충진재를 혼합하여 제조된 시멘트 제품의 압축강도를 표시한 그래프.1 is a graph showing the compressive strength of cement products prepared by mixing the cement composition and each filler of the present invention.
본 발명은 산화마그네슘과 탄산칼슘, 그리고 경화 촉진제로서 수산화바륨을 혼합하여 제조되는 시멘트 조성물에 관한 것이다. 더욱 상세히 말하면 본 발명은 폐기물을 포함하여 어떤 종류의 충진재(filler)와도 강한 결합을 형성하도록 산화마그네슘, 탄산칼슘 및 수산화바륨을 혼합하여 제조되는 시멘트 조성물에 관한 것이다.The present invention relates to a cement composition prepared by mixing magnesium oxide and calcium carbonate and barium hydroxide as a curing accelerator. More specifically, the present invention relates to a cement composition prepared by mixing magnesium oxide, calcium carbonate and barium hydroxide to form a strong bond with any type of filler, including waste.
최근 환경문제가 중대한 사회문제의 하나로 대두되면서 그 해결방법에 대한 여러가지 방안이 연구되고 있다. 해결되어야 할 문제점의 하나로서 폐기물의 처리 및 재활용을 들 수 있다. 이 문제에 관해서는 정부에서도 매스컴을 통하여 연일 강조하고 있지만 성공적인 해결방안의 모색 및 실천의 단계에는 도달하지 못하고 있는 실정이다.Recently, as environmental problems have emerged as one of the serious social problems, various methods for their solutions have been studied. One of the problems to be solved is the disposal and recycling of waste. The government has emphasized this issue through the mass media, but has not reached the stage of finding and implementing a successful solution.
이러한 상황에서 폐기물을 이용하여 산업상 유리한 자원으로 재환용한다면 국가적, 사회적으로 큰 이익이 될뿐만아니라 환경문제의 해결에도 도움이 될 것인바, 이러한 방안들에 대한 요구가 절실하다고 하지 않을 수 없다.In this situation, recycling wastes into industrially beneficial resources will not only benefit nationally and socially, but also help solve environmental problems. The demand for these measures is indispensable.
본 출원인은 이러한 요구에 부응하여 시멘트에 폐기물을 결합시켜 건축자재등으로 재활용하는 방안을 착안하게 되었다. 그러나, 종래의 시멘트는 모래등의 무기물과는 요구되는 요구되는 결합력을 형성하지만 유기물을 포함하여 광범위한 폐기물에 대하여는 강한 결합력을 나타내지 못하였다.In response to this demand, the applicant has come up with a plan to combine waste with cement and recycle it into building materials. However, the conventional cement forms the required bonding force with inorganic substances such as sand, but has not shown strong bonding strength for a wide range of wastes including organic matter.
따라서 본 발명의 목적은 흙, 강모래, 플라이애쉬(flyash)는 물론 버미큘라이트, 톱밥, 쌀겨, 페타이어가루, 제지공장의 슬러지등 모든 종류의 무기물과 유기물에 대해 강한 결합력을 나타내는 시멘트 조성물을 제공하는 것이다.Therefore, an object of the present invention is to provide a cement composition exhibiting a strong binding force against all kinds of inorganic and organic materials such as soil, river sand, flyash, as well as vermiculite, sawdust, rice bran, fetal flour, sludge of paper mills, etc. will be.
상기한 본 발명의 목적은 산화마그네슘(MgO)과 탄산칼슘(CaCO3)를 마그네슘 : 칼슘 중량비가 1 : 10∼1 : 0(바람직하게는 1:1)이 되도록 혼합하고, 경화촉진제로서 산화마그네슘과 탄산칼슘의 총중량이 0-20%(바람직하게는 3-5%)의 수산화바륨을 첨가하여 Ca-Mg시멘트를 제조함으로써 달성될 수 있다.An object of the present invention described above is to mix magnesium oxide (MgO) and calcium carbonate (CaCO 3 ) so that a magnesium: calcium weight ratio is from 1: 10 to 1: 0 (preferably 1: 1), and magnesium oxide as a curing accelerator. The total weight of the calcium carbonate can be achieved by producing Ca-Mg cement by adding 0-20% (preferably 3-5%) of barium hydroxide.
보통 포틀랜드 시멘트는 조성화합물로서 규산 3칼슘(3 CaO·SiO2) 규산 2칼슘(2 CaO·SiO2), 알루민산 3칼슘(3 CaO·Al2O3), 알루민산철 4칼슘(4 CaO·Al2O3·Fe2O3)중의 산화칼슘(CaO)이 물과 반응하여 콜리이드상 수화물을 형성함에 의해 경화하나, 본 발명의 시멘트는 산화마그네슘 성분이 배합시 첨가되는 물과 반응하여 수산화마그네슘(Mg(OH)2)을 형성하고, 또 이들이 공기중의 탄산가스와 결합하여 기경성(氣硬性) 탄산마그네슘(MgCO3)으로서 경화하는 성질을 이용한 것이다.Portland cement is usually composed of tricalcium silicate (3 CaO · SiO 2 ) dicalcium silicate (2 CaO · SiO 2 ), tricalcium aluminate (3 CaO · Al 2 O 3 ), and iron calcium aluminate (4 CaO). Calcium oxide (CaO) in Al 2 O 3 Fe 2 O 3 ) hardens by reacting with water to form a colloidal hydrate, but the cement of the present invention reacts with water added when the magnesium oxide component is added. magnesium hydroxide (Mg (OH) 2) formed, and further they are rigid group (氣硬性) in combination with the carbon dioxide in the air to be using the property of hardening as magnesium carbonate (MgCO 3).
본 발명의 또다른 특징중의 하나는 본 발명의 산화마그네슘은 물 공기중의 탄산가스와 반응하여 탄산마그네슘으로 경화함과 동시에 탄산칼슘과 함께 경화하여 탁월한 결합력을 나타낸다는 것이다.One of the features of the present invention is that the magnesium oxide of the present invention reacts with carbon dioxide gas in water air to cure with magnesium carbonate and at the same time with calcium carbonate to exhibit excellent bonding.
이러한 본 발명의 시멘트는 고체 유기물, 무기물등 어떠한 충진재와도 강한 결합을 형성하며, 수화시 수화열의 방생이 없다. 또 강도면에서도 초기강도는 일반 포틀랜드 시멘트보다 작으나 장기 강도는 더 크다는 장점을 가지고 있다.The cement of the present invention forms a strong bond with any filler, such as solid organics, inorganics, there is no generation of heat of hydration during hydration. In terms of strength, the initial strength is smaller than that of general Portland cement, but the long term strength is higher.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명의 Ca-Mg 시멘트는 하기식과 같이 산화마그네슘과 물이 반응하여 제조된 수산화마그네슘이 공기중의 탄산가스와 반응하여 탄산마그네슘이 되면서 경화되는 성질을 이용한 것이다. 여기에서 수산화바륨은 공기중의 CO2를 끌어들이는 작용을 촉진시킴으로서 경화촉진제의 경화촉진의 역활을 하는 것으로 판단된다.The Ca-Mg cement of the present invention utilizes the property that magnesium hydroxide prepared by reacting magnesium oxide with water reacts with carbon dioxide gas in the air to become magnesium carbonate, thereby curing. Here, barium hydroxide is considered to play a role of promoting the curing of the curing accelerator by promoting the action of attracting CO 2 in the air.
MgO+H2O → Mg(OH)2 MgO + H 2 O → Mg (OH) 2
Mg(OH)2+CO2→ MgCO3+H2OMg (OH) 2 + CO 2 → MgCO 3 + H 2 O
본 발명의 시멘트는 기경성으로서 상기와 같이 공기중의 탄산가스와 결합됨에 따라 시간이 경과할수록 더욱 강한 결합력과 강도를 나타내게 된다.As the cement of the present invention is hardened, as shown above, as the cement is combined with carbonic acid gas in air, the cement exhibits stronger bonding strength and strength as time passes.
특히 본 발명은 수산화바륨를 경화촉진제로 하여 산화마그네슘과 혼합함으로써 천연광물인 백운석(dolomite)과 같은 조성의 강한 결합력을 갖는 합성물질을 형성하는 것으로 추정된다.In particular, the present invention is believed to form a synthetic material having a strong binding force of a composition such as natural mineral dolomite by mixing with magnesium oxide barium hydroxide as a curing accelerator.
본 발명에서 산화마그네슘으로는 마그네사이트(苦灰石)를 약 700-1000℃ 내외의 온도에서 약 20-60분간 하속시켜 제조한 경소(輕燒) 산화마그네슘(MgO 품위 85%)의 미세분말이 사용되며, 탄산칼슘으로는 석회석(CaCO3품위 95%)의 미세 분말이 사용되고, 이때 산화 마그네슘 대 탄산칼슘은 마그네슘 ; 칼슘의 중량비가 1:10∼1:0이 되도록 혼합된다. 바람직하게는, 이 비율은 1:1이다. 이 비율이 1:10 이상이면 제조된 시멘트 제품의 압축강도가 작아지고 이 비율이 1:0이 되면 고가의 산화마그네슘만을 사용하게 되어 전체가격이 상승한다. 산화마그네슘과 탄산칼슘은 통상적인 입자크기를 가질 수 있으나 약 100메시의 것보다 미세한 것이 바람직하고 250메시보다 미세한 것이 더욱 바람직하다. 입자크기가 100메시보다 굵으면 시멘트제품의 성능이 저하된다.In the present invention, as magnesium oxide, fine powder of magnesium oxide (85% MgO grade) prepared by lowering magnesite at a temperature of about 700-1000 ° C. for about 20-60 minutes is used. As the calcium carbonate, fine powder of limestone (95% of CaCO 3 grade) is used, wherein magnesium oxide to calcium carbonate is magnesium; It mixes so that the weight ratio of calcium may be 1: 10-1: 0. Preferably this ratio is 1: 1. If the ratio is greater than 1:10, the compressive strength of the manufactured cement product is reduced, and if the ratio is 1: 0, only expensive magnesium oxide is used, thereby increasing the overall price. Magnesium oxide and calcium carbonate may have customary particle sizes but are preferably finer than those of about 100 mesh and more preferably finer than 250 mesh. If the particle size is thicker than 100 mesh, the performance of the cement product is degraded.
수산화바륨의 산화 마그네슘과 탄산칼슘이 총 중량의 0-20% 비율로 첨가되는데 바람직하게는 이 비율은 3-5%이다. 이 비율이 20% 이상이면 시멘트 및 시멘트 제품이 연화되어 강도가 떨어지고 이 비율이 0%이면 산화마그네슘의 경화속도가 느려져서 경화시간이 많이 소요된다.Magnesium oxide and calcium carbonate of barium hydroxide are added at a ratio of 0-20% of the total weight, preferably 3-5%. If this ratio is more than 20%, the cement and cement products are softened and the strength is decreased. If this ratio is 0%, the curing speed of magnesium oxide is slowed down, which requires a long time for curing.
상기 산화마그네슘, 탄산칼슘 및 수산화바륨의 혼합은 상온(대략 10∼25℃)에서 실시하며 골고루 혼합되도록 한다.Mixing of the magnesium oxide, calcium carbonate and barium hydroxide is carried out at room temperature (approximately 10 to 25 ° C), and evenly mixed.
본 발명의 Ca-Mg시멘트는 충진재와 함께 결합될 수 있다. 충진재로는 흙, 강모래, 플라이애쉬, 버미큘라이트, 톱밥, 쌀겨, 폐타이어가루, 제지공장의 슬러지 등을 포함할 수 있다. 또 그밖의 금속, 비금속을 포함하여 모든 무기물과 유기물을 포함할 수 있다.Ca-Mg cement of the present invention may be combined with the filler. Filling material may include soil, river sand, fly ash, vermiculite, sawdust, rice bran, waste tire powder, sludge of the paper mill and the like. It may also include all inorganic and organic materials, including other metals and nonmetals.
상기 세멘트와 충진재의 배합비율은 1:0 내지 1:5까지 가능하나 1:2인 경우가 가장 바람직하다. 강모래, 흙, 플라이애쉬 등은 중량비로, 버미큘라이트, 톱밥, 쌀겨, 폐타이어가루 등은 용적비로 배합된다.The mixing ratio of the cement and the filler may be 1: 0 to 1: 5, but is most preferably 1: 2. River sand, soil, fly ash and the like are mixed in weight ratio, vermiculite, sawdust, rice bran, waste tire powder and the like in a volume ratio.
물은 수산화마그네슘을 형성시키고 수산화바륨을 용해시켜 충진재에 골고루 분포시키는데 이용된다. 첨가되는 물의 함량은 충진재의 종류에 따라 다르며, 물과 상태에서 반죽의 질기(consistency)가 KSF 2402"포틀랜드 시멘트 콘크리트 슬럼프의 제조방법"에 따라 슬럼프값이 5-10cm가 되는 양으로 첨가된다. 이와같이 제조된 본 발명의 시멘트는 폐기물을 포함하여 각종 충진재와 함께 강한 결합체를 형성하며, 초기 압축 강도는 일반 포틀랜드 시멘트 보다 작으나 상기 압축강도는 더 우수하다.Water is used to form magnesium hydroxide, dissolve barium hydroxide and evenly distribute it in the filler. The amount of water added depends on the type of filler, and the consistency of the dough in water and state is added in an amount such that the slump value is 5-10 cm according to KSF 2402 "Method of manufacturing Portland cement concrete slump". The cement of the present invention thus prepared forms a strong bond with various fillers, including waste, and the initial compressive strength is smaller than that of general Portland cement, but the compressive strength is better.
본 발명의 시멘트 및 시멘트 제품은 일반적인 건축자재를 포함하여 광범위한 분야에 사용될 수 있다.Cement and cement products of the present invention can be used in a wide range of fields, including general building materials.
하기에 실시예는 본 발명 시멘트 조성물 제법에 일례 및 이에따라 제조된 시멘트 제품의 성능을 제시한 것이다. 그러나 이들 실시예는 본 발명을 설명하기 위한 것이며 본 발명의 범위를 제한하려는 것은 아니다.The following examples illustrate the performance of cement products prepared according to the example and the cement composition preparation of the present invention. These examples are, however, intended to illustrate the invention and are not intended to limit the scope of the invention.
실시예 1Example 1
약 250메시크기의 하소된 경소 산화마그네슘(MgO 품위 85%)미세분말 100.0g과 약 250메시크기의 석회석(CaCO3품위 95%)미세분말 134.2g, 및 수산화바륨 11.7g을 프라스틱 용기에 넣고 상온에서 약 5분간 스푼으로 저어 골고루 혼합하였다.100.0 g of calcined light magnesium oxide (85% grade) fine powder of about 250 mesh size and 134.2 g of fine limestone (95% of CaCO 3 grade) fine powder of about 250 mesh size and 11.7 g of barium hydroxide are placed in a plastic container at room temperature. Stir in a spoon for about 5 minutes at evenly mixed.
강모래, 흙, 플라이애쉬, 버미큘라이트, 톱밥, 쌀겨 및 폐타이어가루 등의 충진재는 본 시멘트와의 배합비에 따라 별도의 플라스틱 용기에 담아두었다.Fillers such as steel sand, soil, fly ash, vermiculite, sawdust, rice bran and waste tire powder were placed in separate plastic containers according to the mixing ratio with the cement.
Ca-Mg 시멘트와 각 충전재의 배합비는 다음 표 1과 같다.The mixing ratio of Ca-Mg cement and each filler is shown in Table 1 below.
<표 1>TABLE 1
플라스틱 용기에 만들어진 Ca-Mg 시멘트에, 상기 배합비에 따라 측량하여 둔 충진재를 각각 넣고 스푼으로 잘저어 시멘트와 충진재를 골고루 섞었다.In the Ca-Mg cement made in a plastic container, each of the fillers measured according to the above mixing ratio was put and stirred with a spoon to mix the cement and the filler evenly.
이와같이 방법으로 충진재의 종류에 따라 시멘트와의 배합물을 여러개 제조한 후 물의 양을 달리하면서 반죽의 질기를 측정하였다.In this way, after preparing several formulations with cement according to the type of filler, the hardness of the dough was measured while varying the amount of water.
측정방법은 KSF 2402 "포틀랜드 시멘트 콘크리트의 슬럼프 시험방법"에 의하였으며 시험하여 슬럼프 값이 7cm인 배합물을 선택하였다.The measurement method was based on KSF 2402 "Test method for slump of Portland cement concrete" and a compound having a slump value of 7 cm was selected.
이와같이 선택된 배합물을 모르터 압축강도 시험몰드(50.8cm×50.8cm×50.8cm 입방체)에 넣고 흙손으로 상부 표면을 다듬은 다음 10시간 경과후 몰드를 탈형하여 상온에서 건조시켰다. 건조시간이 각각 3일, 7일, 28일 되었을때에 압축강도 시험기(수동유압식 압축강도 시험기 KDC-12, 정도정밀(주), 경기도 시흥시 시화공단 3나-304)로 압축강도 시험을 하여 제1도와 같은 결과를 얻었다. 이 도면으로부터 Ca-Mg 시멘트는 어떤 충진재와도 우수한 접착력을 형성하며, 기경성로서 공기중의 탄산가스와 작용하여 시간이 경과함에 따라 강도 증가가 크다는 것을 알 수 있다.The selected formulation was placed in a mortar compressive strength test mold (50.8 cm x 50.8 cm x 50.8 cm cube), the top surface was trimmed with a trowel, and after 10 hours, the mold was demolded and dried at room temperature. When the drying time was 3 days, 7 days and 28 days, respectively, the compressive strength test was carried out using a compressive strength tester (manual hydraulic compressive strength tester KDC-12, Jeongdo Precision Co., Ltd., Sihwa Industrial Complex 3na-304). The same result as 1 degree was obtained. It can be seen from this figure that Ca-Mg cement forms excellent adhesion with any filler and acts with carbonic acid gas in the air as a rigid property, so that the strength increases with time.
실시예 2Example 2
충진재로서 흙을 사용하며 시멘트와 흙의 중량비가 1:2가 되도록 하고 시멘트내의 경소산화마그네슘과 석회석의 비율 및 수산화바륨의 첨가비율을 변화시키는 것을 제외하고 실시예 1과 동일한 방법으로 시료를 제조하여 제조후 7일경과시에 압축강도를 측정하였다. 시험결과는 <표 2>에 기재하였다.Samples were prepared in the same manner as in Example 1 except that soil was used as the filler and the weight ratio of cement to soil was 1: 2, and the ratio of magnesium hydroxide and limestone in cement and the addition ratio of barium hydroxide were changed. Compressive strength was measured at 7 days after manufacture. The test results are shown in <Table 2>.
[표 2]TABLE 2
실시예 3Example 3
충진재로서 폐타이어 가루를 사용하는 것을 제외하고 실시예 2와 도일한 실험을 하여 그 결과를 <표 3>에 기재하였다.Except for using waste tire powder as a filler, the same experiment as in Example 2 was carried out and the results are shown in <Table 3>.
[표 3]TABLE 3
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| US7347896B2 (en) | 2000-01-27 | 2008-03-25 | Tececo Pty Ltd | Reactive magnesium oxide cements |
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