KR20180000375A - A Alkali-activated and Aerated building material using blast furnace slag and its preparation method - Google Patents
A Alkali-activated and Aerated building material using blast furnace slag and its preparation method Download PDFInfo
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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
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
- C04B18/142—Steelmaking slags, converter slags
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/24—Producing shaped prefabricated articles from the material by injection moulding
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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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
- C04B20/1077—Cements, e.g. waterglass
- C04B20/1085—Waterglass
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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
- C04B22/02—Elements
- C04B22/04—Metals, e.g. aluminium used as blowing agent
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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
- C04B22/06—Oxides, Hydroxides
- C04B22/062—Oxides, Hydroxides of the alkali or alkaline-earth metals
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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
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
본 발명은 알칼리활성 고로 슬래그 시멘트를 사용하여 제조과정에서 다량의 에너지를 소비하고 온실가스 방출은 물론 환경오염을 가중시키는 포틀랜드 시멘트를 대신하고, 무기단열재로써 경량 기포콘크리트 역할을 할 수 있는 일정한 강도를 유지하면서 에너지 절감효과를 높일 수 있는 경량 기포 건축자재에 관한 것이다.The present invention uses a slag cement with an alkaline active blast as a substitute for Portland cement which consumes a large amount of energy in the manufacturing process and emits not only greenhouse gas but also environmental pollution and has a certain strength to act as lightweight foamed concrete as an inorganic insulator Lightweight air bubble building material which can maintain energy saving while maintaining high efficiency.
최근 들어 전 세계적으로 기후변화에 대응하기 위한 다방면의 노력을 이끌어내고 있으며, 정부에서도 이와 같은 목적으로 온실가스 감축을 위해 2010년 '온실가스 에너지 관리업체 지정 및 관리지침'을 고시하였는데 여기에 시멘트 제조업체도 포함되어 있다. 이것은 시멘트 클링커 제조시 고온(1,450)상태에서 제조될 뿐만 아니라 시멘트 1톤 생산하는데 0.7-1.0톤의 이산화탄소 가스를 배출하게 되는 데 이는 전세계 이산화탄소 가스 배출량의 7%를 차지할 정도로 심각하다. In recent years, the government has been making various efforts to cope with climate change globally. In this regard, the government also announced the 'Guidelines for the designation and management of greenhouse gas energy management companies' in 2010 to reduce greenhouse gas emissions. . This is not only manufactured at the high temperature (1,450) state of cement clinker manufacturing, but also produces 0.7-1.0 tons of carbon dioxide gas to produce one ton of cement, which is 7% of the world's carbon dioxide emissions.
경제발전과 함께 시멘트 산업은 그 규모가 계속 커지고 있으며, 이에 따라 시멘트의 생산과정에서 배출되는 이산화탄소량도 해마다 늘고 있다. 포틀랜드 시멘트 클링커는 현재 인간이 지구에 배출하는 이산화탄소 중에 많은 양을 차지하고 있기 때문에 포틀랜드 시멘트의 대안으로 슬래그 시멘트가 매우 관심을 끌고 있다. With the economic development, the cement industry continues to grow in size, and the amount of carbon dioxide emitted from the production of cement is increasing every year. Portland Cement Clinker is currently attracting much attention as an alternative to portland cement because of the large amount of carbon dioxide emitted by humans on the planet.
한편, 에너지위기 및 환경문제가 대두됨으로서 1997년 일본 교토에서 합의된 지구온난화방지 국제회의에서 2010년 이후 온난화가스 배출량을 선진국의 경우 1990년도 대비 평균 5.2% 감축하는 것을 의무화하고 있다. 따라서 온실가스 배출 규제는 시멘트 업계의 가장 어려운 현안으로 등장할 것으로 판단되며, 향후 이산화탄소 배출이 적은 시멘트를 이용하여 강도가 높은 콘크리트를 제조하는 것이 시급한 문제로 떠오르고 있다. On the other hand, since the energy crisis and environmental problems have arisen, the global warming prevention meeting agreed in Kyoto, Japan in 1997 obliges the developed countries to reduce their greenhouse gas emissions by 5.2% Therefore, regulation of greenhouse gas emission is considered to be the most difficult issue in the cement industry, and it is becoming urgent to manufacture concrete with high strength by using cement with low carbon dioxide emission in the future.
또한, 건축물의 에너지 절감효과 및 공사기간 단축, 다양한 형태로 적용이 가능한 샌드위치 패널로써의 단열재가 많이 사용되고 있다. 샌드위치 패널의 형태로는 유기 및 무기 단열재가 있는데, 유기단열재는 비용이 저렴하다는 장점이 있으나 화재 시 유독가스의 발생으로 인명피해가 크게 발생할 수 있는 반면, 무기계 단열재 중 경량 기포콘크리트는 단열성과 내화성, 경량성 등이 뛰어나기 때문에 샌드위치 패널에 적용하여 유기계의 단점을 해결할 수 있도록 많은 연구가 진행되고 있다. 경량 기포콘크리트는 기포형성제를 활용하여 시멘트 경화체 내에 다량의 공극을 발생시켜 제조한 것으로써 단열성, 내화성, 경량성이 뛰어난 단열자재라고 할 수 있다.In addition, insulation materials such as sandwich panels, which can be applied in various forms, have been widely used for energy saving of buildings, reduction of construction period, and so on. In the form of sandwich panels, there are organic and inorganic insulation materials. Organic insulation materials have the advantages of low cost, but they can cause life damage due to toxic gas in case of fire. Lightweight foamed concrete among inorganic insulation materials, Lightweight, and so on, so that much research has been conducted to solve the drawbacks of the organic system by applying it to the sandwich panel. Lightweight foamed concrete is produced by generating a large amount of voids in cement mortar using bubble formers, which is a good insulation material with excellent heat insulation, fire resistance and light weight.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로서, 제조과정에서 다량의 에너지를 소비하고 온실가스 방출은 물론 환경오염을 가중시키는 포틀랜드시멘트를 대신하여 알칼리활성 고로슬래그시멘트를 사용하기 위한 것으로서, 구체적으로 무기단열재로서 경량 기포콘크리트를 대체할 수 있는 일정한 강도를 가지면서 제조과정 중 에너지 절감효과가 높은 알칼리활성 경량 기포 건축자재를 제공하는 것을 목적으로 한다.The present invention has been made to solve the above problems and it is an object of the present invention to use alkali active blast furnace slag cement in place of portland cement which consumes a large amount of energy during production and emits greenhouse gas as well as environmental pollution, It is an object of the present invention to provide an alkali active lightweight foamed building material having a certain strength to replace lightweight foamed concrete as an inorganic thermal insulator and having a high energy saving effect during the manufacturing process.
본 발명에 따른 알칼리활성 경량 기포 건축자재는 3몰 초과 5몰 미만의 알칼리 활성화제, 기포형성제 및 잔부 고로 슬래그로부터 제조된다. The alkali active lightweight foam building material according to the present invention is prepared from less than 3 molar and less than 5 molar alkali activator, bubbling agent and residual blast furnace slag.
상기 고로슬래그는 비표면적이 4.000~6,000 cm2/g, 비중은 2.5~3.0인 것이 바람직하다. 비표면적이 클수록 반응성은 좋아지지만 이를 위하여 너무 분말도를 높이는 것은 경제적인 점에서 불합리하다.The blast furnace slag preferably has a specific surface area of 4.000 to 6,000 cm 2 / g and a specific gravity of 2.5 to 3.0. The larger the specific surface area, the better the reactivity. However, it is unreasonable in terms of economy to increase the powderity too much for this purpose.
상기 알칼리 활성화제는 3몰 초과 5몰 미만의 것을 사용하는 것이 바람직하며, 3몰 이하인 경우에는 충분한 압축강도를 확보하지 못하고, 5몰 이상인 경우에는 오히려 압축강도가 감소하고 시간이 흐름에 따라 불규칙적으로 증감하기 때문에 바람직하지 않다.The alkali activator is preferably used in an amount of more than 3 moles and less than 5 moles. When the amount of the alkali activator is less than 3 moles, sufficient compressive strength can not be ensured. When the amount of the alkali activator is more than 5 moles, It is not preferable because it increases or decreases.
상기 알칼리 활성화제는 고로슬래그 중량 대비 0.3~0.5 중량%로 첨가하는 것이 바람직하다. 알칼리 활성화제가 0.3 중량% 미만인 경우에는 알칼리 활성화가 충분하지 못하고, 0.5 중량%를 초과하여 첨가하면 오히려 바람직하지 않은 구조와 불균일한 수화물을 생성하기 때문에 바람직하지 않다.The alkali activator is preferably added in an amount of 0.3 to 0.5% by weight based on the weight of the blast furnace slag. When the alkali activating agent is less than 0.3 wt%, the alkali activation is insufficient, and when the alkali activating agent is added in an amount exceeding 0.5 wt%, the structure is undesirable and uneven hydrate is formed.
상기 알칼리 활성화제로는 수산화나트륨과 수산화칼륨 및 보조제로 사용할 수 있으며, 당업자에게 자명한 범위내에서 다른 알칼리 활성화제가 가능하다.As the alkali activating agent, sodium hydroxide, potassium hydroxide and an auxiliary agent can be used, and other alkali activators can be used within a range that is obvious to a person skilled in the art.
상기 기포형성제는 0.05중량% 내지 0.10중량% 이내를 첨가하는 것이 바람직하다. 기포형성제를 0.05중량% 미만으로 첨가하는 경우에는 충분한 다공성이 확보되지 못하고, 0.10중량% 초과하여 첨가하는 경우에는 기포가 합체되어 공극이 크게 형성되는 등의 균일한 다공성을 확보하기가 다소 어렵고, 커진 공극 등으로 인하여 압축강도가 기준미달로 현저히 낮아질 가능성이 있으므로 바람직하지 않다.The bubbling agent is preferably added in an amount of 0.05 to 0.10% by weight. When the bubbling agent is added in an amount of less than 0.05% by weight, sufficient porosity can not be secured. When the bubbling agent is added in an amount exceeding 0.10% by weight, it is somewhat difficult to ensure uniform porosity, It is not preferable because the compressive strength may be significantly lowered due to the large voids and the like.
상기 기포형성제로는 알루미늄 분말을 이용하는 것이 바람직하되 입경이 가능한 작은 것이 좋으며 3um 에서 8um의 분말이 적당하다. 이보다 작은 1um의 분말은 미세한 다공성을 형성하기 좋지만 경제적인 면에서 불리하다. 또, 기포형성제로 과산화수소(H2O2)를 사용할 수 있으나, 당업자에게 자명한 범위내에서 다른 기포형성제의 사용도 가능하다.As the bubbling agent, it is preferable to use an aluminum powder, but it is preferable that the bubble forming agent is as small as possible and a powder of 3um to 8um is suitable. Smaller 1um powder is good for forming fine porosity but is disadvantageous in terms of economy. Hydrogen peroxide (H 2 O 2) may be used as the bubbling agent, but other bubbling agents may be used within the scope that is obvious to a person skilled in the art.
상기 알칼리활성 경량 기포 건축자재는 압축강도가 13N/mm2를 초과하고, 공극율은 55%를 초과한다. 압축강도 등이 기준미달인 경우 건축자재로서 사용이 불가능하다.The alkali active lightweight foam building material has a compressive strength of more than 13 N / mm < 2 > and a porosity of more than 55%. It is impossible to use it as a building material if the compressive strength, etc. is below the standard.
본 발명에 따라 알칼리활성 경량 기포 건축자재를 제조하는 방법은 아래와 같다.A method for producing an alkali active lightweight foamed building material according to the present invention is as follows.
(a) 알칼리 활성화제와 물을 혼합하여 3몰 초과 5몰 미만의 알칼리 활성화 용액을 제조하는 단계;(a) mixing an alkali activating agent and water to produce an alkali activating solution of more than 3 mole but less than 5 moles;
(b) 3몰 초과 5몰 미만의 알칼리 활성화 용액 및 기포형성제와 고로슬래그를 혼합하는 단계; 및(b) mixing less than 3 molar and less than 5 molar alkali activating solution and a bubble former with blast furnace slag; And
(c) 상기 혼합물을 형틀에서 성형하여 기건양생하는 단계.(c) shaping the mixture into a mold and curing the mixture.
이상과 같이 본 발명에 의하면 고로슬래그와 발포제만을 이용하여 고온고압의 증기양생과정 없이 상온에서 단순한 알칼리활성으로 발포시키는 과정으로 경량 발포 소재를 용이하게 제작할 수 있다.As described above, according to the present invention, a lightweight foamed material can be easily manufactured by using only blast furnace slag and a foaming agent, and firing the mixture into a simple alkali activity at room temperature without a high temperature and high pressure steam curing process.
도 1은 수산화나트륨의 농도에 따른 압축강도의 변화를 측정한 것이다.
도 2는 수산화나트륨 4M과 활성화제/슬래그 = 0.4/1.0에 따른 압축강도를 측정한 것이다.
도 3은 기포제가 첨가된 알칼리활성 경량 기포 건축자재의 비중을 측정한 것이다.
도 4는 기포제 첨가량에 따른 압축강도의 변화를 측정한 것이다.
도 5는 본 발명에 따른 알칼리활성 경량 기포 건축자재의 SEM 사진이다.
도 6a 및 도 6b는 알칼리활성화 반응 전후의 XRD 분석 사진이다.Fig. 1 is a graph showing changes in compressive strength depending on the concentration of sodium hydroxide.
Fig. 2 shows the compressive strength measured according to
Fig. 3 is a graph showing the specific gravity of alkali-active lightweight foamed building materials added with foaming agent.
4 is a graph showing changes in compressive strength according to the amount of foaming agent added.
5 is an SEM photograph of an alkali active lightweight foamed building material according to the present invention.
6A and 6B are XRD analysis photographs before and after the alkali activation reaction.
이하, 본 발명의 바람직한 실시 형태를 설명한다. 그러나, 본 발명의 실시 형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다. Hereinafter, preferred embodiments of the present invention will be described. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.
본 발명에 사용된 고로슬래그 미분말은 광양제철 제강과정에서 산업부산물로 발생하는 고로수쇄슬래그(이하 고로슬래그라 칭함)를 사용하였다. 본 발명에 사용되는 고로슬래그의 비표면적은 4,000~6,000 cm2/g이 바람직하며, 하기 실시예에서는 비표면적이 4,234 cm2/g이고 비중은 2.91인 것을 사용하였다. 고로슬래그의 화학적 조성은 하기 표 1에 나타내었다. 고로슬래그의 화학분석 결과 CaO 43.9%와 SiO2 32.8%를 주성분으로 하여 Al2O3 14.9%, MgO 5.0%를 포함하며, 유리화 율이 높고 결정이 적은 수재슬래그로서 수경성이 높은 멜릴라이트(Mellilite)계이다.The blast furnace slag used in the present invention is blast furnace slag (hereinafter referred to as blast furnace slag) which is generated as an industrial by-product in the steelmaking process of Gwangyang steel mill. The blast furnace slag used in the present invention preferably has a specific surface area of 4,000 to 6,000 cm 2 / g and a specific surface area of 4,234 cm 2 / g and a specific gravity of 2.91 in the following examples. The chemical composition of the blast furnace slag is shown in Table 1 below. As a result of the chemical analysis of blast furnace slag, it was found that the slag containing 43.9% of CaO and 32.8% of SiO 2 as main components, containing 14.9% of Al 2 O 3 and 5.0% of MgO and having high vitrification rate and low crystallinity, System.
Mix ratio design
본 발명의 고로슬래그의 알칼리 활성반응을 위한 알칼리 활성화제로서 공업용 수산화나트륨(순도 98 wt%)을 물에 용해하여 2M~5M의 NaOH 용액을 제조한 후, 최적의 고로슬래그 배합비와 NaOH의 함량을 결정하였다.As an alkali activator for alkali activation reaction of the blast furnace slag of the present invention, industrial sodium hydroxide (purity: 98 wt%) was dissolved in water to prepare a 2M to 5M NaOH solution, and then an optimum blast furnace slag mixing ratio and NaOH content .
본 발명의 알칼리활성 경량 기포 건축자재의 시편을 제작하기 위해 상기에서 준비한 활성화용액과 고로슬래그를 호바트(Horbart) 믹서를 이용하여 저속으로 반죽하여 혼합하였다. 시편 제작을 위해 사용된 공시체는 가로 50㎜, 세로 50㎜, 높이 50mm의 직육면체형 콘크리트용 몰드를 사용하였다. 몰드 내부에 실리콘 그리스를 얇게 바른 후 세팅하여 시료를 몰드에 채운 후 각각 25회씩 다짐하였으며 최상층을 다진 후 흙손으로 콘크리트면을 고르게 하여 캡핑하였다(KS F 2403). 몰드에 시료를 채운 후 봉다짐을 하게 되는데 봉다짐 숙련도에 따라 압축강도가 영향을 받으므로 한 사람이 봉다짐을 하였다. 캡핑 한 후 1일간 상온 공기 중에서 활성화 한 다음, 탈형하여 압축강도 측정일까지 상온에서 기건양생 방법을 택하여 시편을 제작하였다.In order to prepare specimens of the alkali active lightweight foamed building material of the present invention, the activating solution and the blast furnace slag prepared above were kneaded at a low speed using a Hobart mixer and mixed. The specimens used for making specimens were rectangular molds with a width of 50 mm, a length of 50 mm and a height of 50 mm. The mold was filled with a sample of silicone grease by thin layer of silicone grease. The mold was filled 25 times each time. The top layer was chopped and then the concrete surface was capped with trowel (KS F 2403). After filling the mold with the specimen, it was tightened. As the compressive strength was influenced by the sealing strength, one person was sealed. After capping, it was activated in air at room temperature for 1 day. Then, demolding was performed, and specimen was prepared by curing curing method at room temperature until the measurement of compressive strength.
알칼리활성 경량 기포 건축자재의 시편을 제조하는데, 적정한 압축강도 발현을 위해 하기 표와 같이 알칼리활성화제 농도를 2~5M로 변화시키고, 알칼리활성화제/고로슬래그 배합비를 0.3~0.5/1.0 중량비로 변경시켜 적용하였다. 이와 같이 제조된 시편을 상온에서 1-28 일간 기건양생 하였다.The alkali activator concentration was varied from 2 to 5 M and the alkali activator / blast furnace slag composition ratio was changed from 0.3 to 0.5 / 1.0 weight ratio as shown in the following table for proper compression strength development in the production of alkali active lightweight foam building materials. Respectively. The specimens were cured at room temperature for 1-28 days.
Alkali activator / blast furnace slag (wt% ratio)
1.0
상기에 알칼리활성 경량 기포 건축자재의 시편을 KS F 2405에 준하여 압축강도를 측정하였다. 일축압축강도 시험장비는 United Calibrafun Co.가 제작한 STM-5 모델의 만능재료시험기(UTM)를 사용하였으며 하중은 100ton까지 측정이 가능하며 변위는 0.01㎜까지 측정 할 수 있다. 측정에 사용된 시편은 측정시 마다 3개의 시편을 제작하여, 100 ton 용량의 일축 압축시험기를 사용하여 매초 약 0.2N/mm2(2.04 kgf/cm2)의 속도로 압축강도를 측정한 후, 파괴강도 ± 5% 이상인 자료는 제외하고 평균하여 압축강도를 산출하였다.The compressive strength of the alkali active lightweight foam building material was measured according to KS F 2405. The uniaxial compressive strength test equipment is a universal material testing machine (UTM) of STM-5 model manufactured by United Calibrafun Co. The load can be measured up to 100ton and the displacement can be measured up to 0.01mm. Three specimens were prepared for each measurement and the compressive strength was measured at a rate of about 0.2 N / mm 2 (2.04 kgf / cm 2 ) per second using a 100 ton unconfined compression tester. Compressive strength was calculated by averaging excluding data with a breaking strength of ± 5% or more.
도 1에서 볼 수 있듯이 상온에서 1에서 28일간 기건양생하여 제조한 시편의 경우 수산화나트륨의 농도가 증가 할수록 압축강도는 점진적으로 증가하는 것으로 나타났으며, 4M의 농도에서의 압축강도가 시간이 지남에 따라 압축강도가 증가하는 경향이 뚜렷하게 나타나는 것으로 보아 알칼리활성화제의 적정 첨가량은 3~5M임을 알 수 있었다. 이러한 결과는 활성화제의 첨가량이 증가함에 따라 상대적으로 일정한 물의 양에 비해 수산화나트륨의 농도가 증가되면서 시편의 알칼리 활성화 반응을 촉진하는 결과로 해석되며 이로 인해 충분한 양의 활성 반응생성물이 생성되었기 때문으로 판단된다. 수산화나트륨의 농도를 5M 이상으로 증가시켜 제조한 시편의 경우 오히려 압축강도가 감소하고 또한 시간이 지남에 따라 압축강도는 불규칙적으로 증가, 감소하는 경향을 보였는데 이것은 수산화나트륨과 고로슬래그의 알칼리 활성반응을 위해서는 수산화나트륨용액 3~5M일 경우가 압축강도의 발현 측면에서 가장 적합한 것으로 나타났다. 일반적으로 고로슬래그의 알칼리 활성반응을 위해 과도한 NaOH를 첨가할 경우 오히려 시편 내에 바람직하지 않는 구조와 불균일한 수화물을 생성하기 때문으로 NaOH를 일정량 이상 첨가할 경우 뚜렷한 강도증가는 없는 것으로 판단된다.As can be seen in FIG. 1, the compressive strength of the specimens prepared by curing at room temperature for 1 to 28 days was found to increase gradually with increasing sodium hydroxide concentration. Compressive strength at 4M concentration increased over time The compressive strength tends to increase with increasing the amount of alkali activator. The optimum amount of alkali activator was 3 ~ 5M. This result is interpreted as a result of increasing the concentration of sodium hydroxide compared to a relatively constant amount of water as the amount of activator added increases, thereby promoting the alkali activation reaction of the sample, . The compressive strength of the specimens prepared by increasing the concentration of sodium hydroxide to 5M or more decreased and the compressive strength of the specimens increased irregularly with time. This showed that the alkali activity of sodium hydroxide and blast furnace slag , The optimum concentration of sodium hydroxide solution was 3 ~ 5M in terms of compressive strength. In general, when excess NaOH is added to the alkali activated reaction of blast furnace slag, it causes undesirable structure and uneven hydrate in the specimen. Therefore, it is considered that there is no significant increase in strength when NaOH is added over a certain amount.
시멘트 물질에 있어서 압축강도는 가장 중요한 평가 항목이다. 알칼리활성 경량 기포 건축재의 제조를 위한 슬래그는 100% 고로슬래그를 사용하였으며, 다양한 농도의 알칼리활성화제와 고로슬래그의 배합 비율을 이용하여 시편을 제작한 결과, 활성화제로써 수산화나트륨을 이용한 수재슬래그의 알칼리활성 반응을 위해서는 활성화제/슬래그 = 0.3~0.5/1.0이 강도발현에 가장 적정한 배합 조건임을 알 수 있었다(도1 및 도 2).The compressive strength of cementitious materials is the most important evaluation item. The slag used for the production of alkali active lightweight foamed construction material was 100% blast furnace slag. The specimens were prepared by using blend ratio of alkali activator and blast furnace slag with various concentrations. As a result, It was found that the activator / slag = 0.3-0.5 / 1.0 is the most appropriate mixing condition for the intensity activation for the alkali activation reaction (FIGS. 1 and 2).
한편, 알칼리활성 경량 기포 건축자재의 비중을 기포제인 알루미늄의 첨가량에 따라 측정한 결과를 도 3에 나타내었다. 기포제가 첨가되지 않았을 경우의 비중이 1.9인데 비해 기포제의 양이 0.05중량%, 0.1중량%, 0.15중량%로 증가했을 경우 각각 1.33, 1.29, 그리고 1.15로 감소함을 알 수 있었다. Meanwhile, FIG. 3 shows the results of measurement of the specific gravity of the alkali active lightweight foamed building material according to the addition amount of aluminum foaming agent. It was found that the specific gravity when the foaming agent was not added was 1.9, whereas when the amount of foaming agent was increased to 0.05 wt%, 0.1 wt% and 0.15 wt%, it decreased to 1.33, 1.29 and 1.15, respectively.
따라서, 적합한 기포제의 함량을 결정하기 위해 기포제의 첨가량에 따른 압축강도의 변화에 대한 실험을 하였다. 도 4의 결과에서 알 수 있듯이 알칼리활성 경량 기포 건축자재의 압축강도에 대한 KS 규격인 13N/mm2을 만족하는 기포제의 함량은 0.05~0.10%임을 알 수 있었다.Therefore, in order to determine the content of a suitable foaming agent, an experiment was conducted on the change of compressive strength according to the amount of foaming agent added. As can be seen from the results in FIG. 4, the content of the foaming agent satisfying the KS standard 13 N / mm 2 against the compressive strength of the alkali active lightweight foamed building material was found to be 0.05 to 0.10%.
또한, 알칼리활성화제인 NaOH의 농도를 4M로 하고 기포제의 함량을 0.1%로 하여 시편을 제조한 후 알칼리활성 경량 기포 건축자재의 흡수율과 공극율을 측정한 결과 흡수율을 21.1%였으며 공극율을 55.5%임을 알 수 있었다. 흡수율이 21.1%로 측정된 것은 기포제의 의해 형성된 기포의 영향으로 생긴 공극이 원인인 것으로 사료된다.The water absorption and porosity of the alkali-activated lightweight foamed building materials were measured to be 21.1% and 55.5%, respectively, after the specimens were prepared with the concentration of NaOH, the alkali activator, of 4M and the foaming agent content of 0.1% I could. It is considered that the reason why the absorption rate is 21.1% is caused by the void caused by the bubble formed by the foaming agent.
나아가, 도 5는 알칼리활성 반응을 통하여 얻어진 알칼리활성 경량 기포 건축자재 표면의 SEM 이미지이다. SEM 이미지로부터 비표면적이 3,000㎠/g이상의 고로슬래그 미분말을 알칼리활성화 한 결과 미분형태 입자는 거의 발견되지 않고 새로운 치밀한 형태의 표면을 보여주고 있다. 이것은 알칼리 활성제로 사용되는 NaOH 용액에 의해 야기되는 높은 pH하에서 미분형태의 고로슬래그가 화학반응을 통하여 용해된 후 재결합하였음을 의미한다. 이러한 과정을 통하여 고로슬래그에 포함된 CaO와 SiO2 및 Al2O3 등이 시멘트와 유사한 포졸란반응을 일으켜 에트린자이트(ettringite)를 형성시키면서 치밀한 구조로 변화되어 압축강도를 발현시키게 되는 것을 알 수 있다.Further, FIG. 5 is an SEM image of the surface of the alkali active lightweight foamed building material obtained through the alkali activation reaction. As a result of alkali activation of the blast furnace slag with a specific surface area of 3,000 cm2 / g or more from the SEM image, the fine powder particle is hardly detected and shows a new dense surface. This means that under high pH caused by the NaOH solution used as an alkaline activator, the blast-shaped blast-furnace slag was dissolved via chemical reaction and recombined. Through this process, CaO, SiO2 and Al2O3 contained in the blast furnace slag react with cement-like pozzolanic reaction to form ettringite, which is converted to a dense structure, and the compressive strength is exhibited.
마지막으로, 도 6a는 알칼리활성반응물에 대한 XRD 결과이며 도 6b는 이와 비교하기 위해 분석한 반응전 슬래그의 XRD 분석결과이다. 그림으로부터 원 슬래그의 XRD 결과는 비교적 단순한 패턴을 보이고 있으나, 반응후에 얻어진 결과는 좀더 복잡하고 다양한 피크의 형태를 나타내고 있는 것을 알 수 있다. 여기서 다양한 피크는 알칼리활성반응을 통하여 분말형태의 슬래그가 높은 pH에서 용해된 후 이온들의 화학적 결합과 반응을 통하여 굳어지면서 새로운 결정형태가 생성된 것으로 판단된다. NaOH 용액을 활성화제로 첨가한 혼합물의 조건에 따라 형성된 높은 pH에서 슬래그분말로부터 용해된 이온의 형태는 슬래그에 포함된 화학적 구성 성분 중 가장 많은 비율을 차지하고 있는 SiO2, 그리고 CaO 및 Al2O3와 같은 화학종이다. 이들은 이온상태에서 발열반응과 함께 화학반응이 진행되면서 포졸란반응을 통한 일부의 수산화물형성과 증발과정을 통하여 수분이 제거되는 과정을 통하여 건조하고 단단한 새로운 형태의 결정이 성장하게 되는 것으로 판단된다. Finally, FIG. 6A is the XRD result for the alkali active reactant, and FIG. 6B is the XRD analysis of the slag before the reaction analyzed for comparison. From the figure, it can be seen that the XRD results of the original slag show a relatively simple pattern, but the results obtained after the reaction show more complex and various peak shapes. Here, the various peaks were found to be formed by dissolving the powdery slag at high pH through alkali activation reaction and then solidifying through chemical bonding and reaction of ions. The form of dissolved ions from the slag powder at high pH, which is formed according to the conditions of the mixture of NaOH solution and activator, is SiO2, which is the largest proportion of the chemical constituents in the slag, and chemical species such as CaO and Al2O3 . It is believed that these ions grow in the ionic state as the reaction with the exothermic reaction progresses, and through the pozzolanic reaction, some hydroxide formation and evaporation process removes the moisture, and a new type of dry and hard crystal grows.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, It will be obvious to those of ordinary skill in the art.
Claims (9)
Alkali-active lightweight foam building materials made from compositions of less than 3 moles and less than 5 moles of alkali activators, bubblers, and remainder blast furnace slag
2. The alkali-active lightweight foamed building material according to claim 1, wherein the blast furnace slag has a specific surface area of 4.000 to 6,000 cm < 2 > / g and a specific gravity of 2.5 to 3.0.
The alkali activated lightweight foamed building material according to claim 1, wherein the alkali activator is contained in an amount of 0.3 to 0.5% by weight
The alkali activated lightweight foamed building material according to claim 1, wherein the alkali activator is at least one selected from sodium hydroxide, potassium hydroxide and water glass
An alkali activated lightweight foamed building material according to claim 1, characterized in that it comprises 0.05 to 0.10% by weight of the bubble former
The bubble generator as claimed in claim 1, wherein the bubbling agent is aluminum or hydrogen peroxide.
7. The alkali-active lightweight foamed building material according to claim 6, wherein the aluminum is 3um to 8um powder
The alkali activated lightweight foamed building material according to claim 1, wherein the alkali active lightweight foamed building material has a compression strength of more than 13 N / mm < 2 > and a porosity of more than 55%
(b) 3몰 초과 5몰 미만의 알칼리 활성화 용액 및 기포형성제와 고로슬래그를 혼합하는 단계; 및
(c) 상기 혼합물을 형틀에서 성형하여 기건양생하는 단계를 포함함을 특징으로 하는 알칼리활성 경량 기포 건축 자제의 제조방법
(a) mixing an alkali activating agent and water to produce an alkali activating solution of more than 3 mole but less than 5 moles;
(b) mixing less than 3 molar and less than 5 molar alkali activating solution and a bubble former with blast furnace slag; And
(c) molding the mixture in a mold and curing the mixture to form a lightweight foamed structure.
Priority Applications (1)
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102075289B1 (en) * | 2019-01-23 | 2020-02-07 | 부산대학교 산학협력단 | Ultra lightweight cement composition and method of preparing thereof |
CN112898045A (en) * | 2021-03-31 | 2021-06-04 | 成渝钒钛科技有限公司 | High-titanium blast furnace slag porous sound-absorbing ceramic and preparation method thereof |
CN113264717A (en) * | 2021-06-11 | 2021-08-17 | 东北大学 | Large-mixing-amount solid waste base-activated foam concrete and preparation method thereof |
KR20230003668A (en) * | 2021-06-28 | 2023-01-06 | 박태원 | Ceramic composite binder composition having cohesive with curable and method for manufacturing a bubble foam matrix curing at room temperature |
-
2016
- 2016-06-22 KR KR1020160077977A patent/KR20180000375A/en not_active Application Discontinuation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102075289B1 (en) * | 2019-01-23 | 2020-02-07 | 부산대학교 산학협력단 | Ultra lightweight cement composition and method of preparing thereof |
CN112898045A (en) * | 2021-03-31 | 2021-06-04 | 成渝钒钛科技有限公司 | High-titanium blast furnace slag porous sound-absorbing ceramic and preparation method thereof |
CN113264717A (en) * | 2021-06-11 | 2021-08-17 | 东北大学 | Large-mixing-amount solid waste base-activated foam concrete and preparation method thereof |
CN113264717B (en) * | 2021-06-11 | 2023-03-21 | 东北大学 | Large-mixing-amount solid waste base-activated foam concrete and preparation method thereof |
KR20230003668A (en) * | 2021-06-28 | 2023-01-06 | 박태원 | Ceramic composite binder composition having cohesive with curable and method for manufacturing a bubble foam matrix curing at room temperature |
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