KR20200060096A - Method for manufacturing of carbon nanotubes blend cement using technology of agglutination between cement and multi-walled carbon nanotubes - Google Patents

Method for manufacturing of carbon nanotubes blend cement using technology of agglutination between cement and multi-walled carbon nanotubes Download PDF

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KR20200060096A
KR20200060096A KR1020180145628A KR20180145628A KR20200060096A KR 20200060096 A KR20200060096 A KR 20200060096A KR 1020180145628 A KR1020180145628 A KR 1020180145628A KR 20180145628 A KR20180145628 A KR 20180145628A KR 20200060096 A KR20200060096 A KR 20200060096A
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mwcnts
cement
clinker
silo
cnt
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김학영
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단국대학교 산학협력단
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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
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
    • C04B7/42—Active ingredients added before, or during, the burning process
    • C04B7/421—Inorganic materials
    • 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
    • C04B11/00—Calcium sulfate cements
    • C04B11/28—Mixtures thereof with other inorganic cementitious materials
    • C04B11/30—Mixtures thereof with other inorganic cementitious materials with hydraulic cements, e.g. 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
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/48—Clinker treatment
    • C04B7/52—Grinding ; After-treatment of ground cement
    • C04B7/522—After-treatment of ground cement

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The present invention provides a method for manufacturing CNT agglutination type mixed cement. The method comprises the steps of: (a) processing multi-walled carbon nanotubes (MWCNTs) in a MWCNT processing unit (100); (b) blending the treated MWCNTs and cement raw materials in a raw material silo (210); (c) preheating the blended MWCNTs and the cement raw materials in a preheater (220), and plasticizing the blended MWCNTs and the cement raw materials in a plasticizing device (230) to produce a cement clinker, and transferring the cement clinker to a clinker silo (240); (d) adding plaster to the cement clinker in the clinker silo (240) and transferring the cement clinker to which the plaster is added to a crusher (250); and (e) crushing the cement clinker to which the plaster is added in the crusher (250), and transferring the crushed cement clinker to a cement silo (260). The step (a) comprises the steps of: (a1) preprocessing MWCNTs using a N-methyl-2-pyrrolidone (NMP) solvent and a lecithin surfactant to remove van der Waals forces by a MWCNT pretreatment part (110); (a2) adding a carboxyl group (COOH) to apply a reflux method to the pretreated MWCNTs by a MWCNTs reflux application part (120); and (a3) adding the MWCNTs to which the carboxyl group is added to crystallized minerals in a MWCNT crystallization part (130). Accordingly, the CNT agglutination type mixed cement capable of preventing cracking can be manufactured.

Description

MWCNTs와 시멘트의 결합을 통한 CNT 교착형 혼합시멘트 제조 방법{Method for manufacturing of carbon nanotubes blend cement using technology of agglutination between cement and multi-walled carbon nanotubes}{Method for manufacturing of carbon nanotubes blend cement using technology of agglutination between cement and multi-walled carbon nanotubes}

본 발명은 건설재료에 관한 것으로, 구체적으로 MWCNTs와 시멘트 클링커의 건식 결합을 통한 CNT 교착형 혼합시멘트 제조 방법에 관한 것이다. The present invention relates to a construction material, specifically, to a method of manufacturing a CNT interlocking type mixed cement through dry bonding of MWCNTs and cement clinker.

건설재료로서 콘크리트는 전 세계에 걸쳐 연간 약 110억 톤 이상이 사용되고 있는 핵심재료로 평가된다. 그러나 콘크리트의 본질적인 취약점인 취성파괴와 이로 인한 낮은 파괴인성, 그리고 수축으로 인한 균열 등은 여전히 불가피한 단점으로 지적되고 있다.As a construction material, concrete is estimated to be a core material that is used more than 11 billion tons per year worldwide. However, brittle fracture, which is an essential weakness of concrete, and its low fracture toughness and crack due to shrinkage, are still pointed out as inevitable disadvantages.

탄소나노튜브(CNTs; Carbon Nano Tubes)는 탄소원자로만 이루어진 그래핀(graphene)막을 롤업(roll-up)하여 나노 규모의 직경을 갖는 튜브의 형태로 제조된 재료이다. 이는 단일막을 사용한 Single-Walled CNT(SWCNT)와 다중막을 사용한 Multi-Walled CNTs(MWCNTs)로 각각 구분되며, 관련 산업에서는 주로 MWCNTs가 활용되고 있다.Carbon nanotubes (CNTs) are materials manufactured in the form of tubes having a nano-scale diameter by rolling up a graphene film made of only carbon atoms. It is divided into single-walled CNTs (SWCNT) using single membranes and multi-walled CNTs (MWCNTs) using multiple membranes, and MWCNTs are mainly used in related industries.

MWCNTs는 낮은 밀도(0.2∼1.33g/cm3)에도 불구, 약 1.0TPa의 탄성계수와 20∼60GPa 수준의 항복강도를 갖는 기계적 우월성을 이유로 콘크리트 등 시멘트 복합체의 미세 섬유보강재로서 각광을 받고 있다. Despite its low density (0.2 to 1.33 g / cm3), MWCNTs are in the spotlight as fine fiber reinforcements for cement composites such as concrete because of their mechanical superiority with an elastic modulus of about 1.0 TPa and a yield strength of 20 to 60 GPa.

그러나, 압축강도 200MPa를 발휘할 수 있는 극초고강도 콘크리트를 생산하거나, 균열발생을 억제할 수 있는 MWCNTs 혼입 콘크리트의 제조를 위해서는 CNTs가 갖고 있는 엉킴 및 뭉침 현상에 대한 해결방안이 요구된다. However, in order to produce ultra-high strength concrete capable of exerting a compressive strength of 200 MPa, or to manufacture MWCNTs mixed concrete capable of suppressing cracking, a solution to the entanglement and aggregation phenomenon of CNTs is required.

CNTs는 수성물질보다 유성물질과의 친화력이 큰 무극성 및 소수성(hydrophobic)을 지닌 물질이나, 물을 포함하는 재료 내에서는 입자들 간의 반데르발스 힘(Van der Waals force)이 작용되어 엉킴 및 뭉침 현상이 나타나게 된다(도 1의 좌측도면 참조). 더욱이, CNTs와 같은 나노 스케일 단계의 엉킴 현상은 육안으로는 확인이 불가할 뿐만 아니라 미세현미경 등의 장비를 이용할 경우에도 정량적 성능평가는 매우 곤란한 실정이다.CNTs are nonpolar and hydrophobic substances that have more affinity with oily substances than aqueous substances, but in materials containing water, van der Waals force between particles acts to entangle and clump. Will appear (see left drawing in FIG. 1). Moreover, the entanglement of nanoscale steps such as CNTs cannot be confirmed with the naked eye, and quantitative performance evaluation is very difficult even when using equipment such as a microscopic microscope.

기존 연구에서는 주로 시멘트의 경화 이전단계인 재료의 혼합과정(fresh concrete)에서 아세톤이나 에탄올 등의 용제를 추가 혼입하는 기법과 혼합수에 계면활성제(surfactant)와 CNTs를 동시 혼입하는 기법, 그리고 물리적 외력인 초음파(sonication) 처리를 통해 나노 재료의 물성을 변화시키려는 등의 다양한 노력이 있어왔다. In the existing studies, a technique of adding a solvent such as acetone or ethanol in a fresh concrete, which is mainly a step prior to curing of cement, a technique of simultaneously mixing surfactants and CNTs in the mixed water, and physical external force Various efforts have been made to change the physical properties of nanomaterials through phosphorus sonication.

그러나 CNTs의 분산효과 적용 후 경과시간 수분 내에 혼합수와 계면활성제 그리고 CNTs의 밀도 차이에 의한 침전현상이 나타났을 뿐만 아니라(도 1의 우측도면 참조), 여러 공정의 전처리 문제 및 CNTs의 과도한 혼입률(혼입량을 증가시킴으로서 분산문제를 해결하려 함)로 인해 경제성에 대한 한계를 드러냈다. However, after the dispersion effect of CNTs was applied, precipitation was observed due to the difference in density between mixed water, surfactant, and CNTs within minutes of elapsed time (see the right figure of FIG. 1), pretreatment problems of various processes, and excessive mixing rate of CNTs ( The attempt to solve the variance problem by increasing the amount of mixing) revealed limitations on economic efficiency.

관련된 특허문헌을 검토한다. Review related patent documents.

한국특허공개 제10-2013-0083649호는 탄소나노튜브를 함유한 시멘트 복합재료의 제조방법과 이 시멘트 복합재료를 이용한 탄소나노튜브-시멘트 구조체의 제조방법을 개시한다. 구체적으로, 분산성능이 낮은 탄소나노튜브를 시멘트에 혼합하여 시멘트 복합재료를 제조하기 위해, 나노소재인 실리카퓸을 활용한 물리적인 분산 방법과, 탄소나노튜브와 실리카퓸과 시멘트를 혼합하여 건비빔된 혼합물에 물과 폴리카르복실산계 초유동화제를 첨가하는 방법을 제안한다. Korean Patent Publication No. 10-2013-0083649 discloses a method of manufacturing a cement composite material containing carbon nanotubes and a method of manufacturing a carbon nanotube-cement structure using the cement composite material. Specifically, in order to prepare a cement composite material by mixing carbon nanotubes having low dispersing performance in cement, a physical dispersion method using silica fume, a nanomaterial, and dry mixing by mixing carbon nanotubes, silica fume and cement It is proposed to add water and a polycarboxylic acid-based superfluidizing agent to the mixture.

한국특허공개 제10-2012-0139959호는 고밀도 나노 코팅 조성물을 제안한다. 이는, 무기질 재료에 소수성을 제공하여, 분산성, 방청성, 내한성, 기계적 강도, 내수성, 접착성, 신축성 및 압축성을 부여한 것으로, 폴리카르복실레이트 등의 군으로부터 선택되는 1종 이상을 총 중량비에 대해서 0.04∼2중량％ 함유하는 방법을 제안한다.Korean Patent Publication No. 10-2012-0139959 proposes a high density nano coating composition. This provides hydrophobicity to the inorganic material, imparting dispersibility, rust resistance, cold resistance, mechanical strength, water resistance, adhesion, elasticity, and compressibility, and one or more selected from the group of polycarboxylates, etc., based on the total weight ratio A method of containing 0.04 to 2% by weight is proposed.

일본특허공개 제2013-086275호는 시멘트 경화체 제조 방법을 개시한다. 탄소 나노튜브를 적합하게 분산시켜 시멘트 경화체를 고강도화하는 것을 가능하게 한 시멘트 경화체 제조 방법을 제공하기 위해, 시멘트와 탄소 나노튜브를 건식 조건에서 혼합하고, 응집 상태의 탄소 나노튜브를 해쇄하고, 시멘트 입자의 표면에 모사구슬과 같은 상태에서 부착시켜 복합 입자 상태의 혼합체를 형성하는 방법을 제안한다.Japanese Patent Publication No. 2013-086275 discloses a method for manufacturing a cement cured body. Cement and carbon nanotubes are mixed under dry conditions to disintegrate carbon nanotubes in a dry condition to disintegrate carbon nanotubes to provide a method for producing a cement hardened body, thereby crushing the agglomerated carbon nanotubes and cement particles. It proposes a method of forming a mixture in the form of a composite particle by attaching it to the surface of a yarn in the same state as a yarn ball.

한국특허공개 제10-2013-0083649호Korean Patent Publication No. 10-2013-0083649 한국특허공개 제10-2012-0139959호Korean Patent Publication No. 10-2012-0139959 일본특허공개 제2013-086275호Japanese Patent Publication No. 2013-086275

본 발명은 상기와 같은 문제점을 해결하기 위하여 안출된 것이다. The present invention has been devised to solve the above problems.

구체적으로, 시멘트의 제조공정에서 MWCNTs를 시멘트 분말과 교착화시켜 MWCNTs 일체형 혼합시멘트를 제조함으로서 엉킴의 요인을 원천적으로 제거하는 방법을 제안하고자 한다. Specifically, in the process of manufacturing cement, MWCNTs are interlocked with cement powder to manufacture a mixed cement of MWCNTs to propose a method of fundamentally removing the factors of entanglement.

특히, MWCNTs가 갖고 있던 엉킴 및 뭉침 현상을 방지하는 기술을 채택하여, 극초고강도 콘크리트를 생산하거나, 균열발생을 억제할 수 있는 CNT 교착형 혼합시멘트의 제조 방법을 제안하고자 한다. In particular, by adopting the technology to prevent the entanglement and agglomeration phenomenon that MWCNTs had, it is intended to propose a method for producing CNT interlocking type mixed cement that can produce ultra-high strength concrete or suppress cracking.

상기와 같은 과제를 해결하기 위한 본 발명의 일 실시예는, (a) MWCNTs(Multi-Walled Carbon Nano Tubes) 처리부(100)에서 MWCNTs를 처리하는 단계; (b) 원료 사일로(210)에서, 상기 처리된 MWCNTs와 시멘트 원료가 블렌딩되는 단계; (c) 상기 블렌딩된 MWCNTs와 시멘트 원료가 예열기(220)에서 예열되고 소성기(230)에서 소성되어 시멘트 클링커가 생성된 후, 클링커 사일로(240)로 이송되는 단계; (d) 상기 클링커 사일로(240)에서 상기 시멘트 클링커에 석고가 추가되어 분쇄기(250)로 이송되는 단계; 및 (e) 상기 분쇄기(250)에서, 상기 석고가 추가된 시멘트 클링커가 분쇄된 후 시멘트 사일로(260)로 이송되는 단계를 포함하며, 상기 (a) 단계는, (a1) MWCNTs 전처리부(110)가 반데르발스 힘을 제거하도록 NMP(N-methyl-2-pyrrolidone) 용제와 레시틴(Lecithin surfactant)을 이용하여 MWCNTs를 전처리하는 단계; (a2) MWCNTs 환류적용부(120)가 상기 전처리된 MWCNTs에 환류법을 적용하도록 카르복실기(COOH)를 부여하는 단계; 및 (a3) MWCNTs 결정화부(130)에서 결정화 광물에 상기 카르복실기가 부여된 MWCNTs를 투입하여, 상기 MWCNTs를 처리하는 단계를 포함하는, CNT 교착형 혼합시멘트 제조 방법을 제공한다.One embodiment of the present invention for solving the above problems, (a) MWCNTs (Multi-Walled Carbon Nano Tubes) processing unit 100 in the MWCNTs process; (b) in the raw material silo 210, blending the treated MWCNTs with a cement raw material; (c) after the blended MWCNTs and cement raw material are preheated in a preheater 220 and fired in a calciner 230 to generate a cement clinker, then transferred to a clinker silo 240; (d) gypsum is added to the cement clinker in the clinker silo 240 and transferred to the grinder 250; And (e) in the pulverizer 250, the cement clinker to which the gypsum is added is crushed, and then transferred to a cement silo 260, wherein the step (a) comprises: (a1) MWCNTs pretreatment unit 110 Pretreatment of MWCNTs using NMP (N-methyl-2-pyrrolidone) solvent and Lecithin surfactant to remove van der Waals forces; (a2) MWCNTs reflux application unit 120 is applied to the pre-treated MWCNTs to give a carboxyl group (COOH) to apply the reflux method; And (a3) MWCNTs crystallization unit 130, the carboxyl group is added to the MWCNTs is added to the crystallized mineral, comprising the step of treating the MWCNTs, provides a method for producing a CNT hybrid mixed cement.

또한, 상기 (a3) 단계에서의 상기 결정화 광물은 카올리나이트(Kaolinite, Al2Si2O5(OH)4) 또는 멀라이트(Mullite, 3Al2O3SiO2)인 것이 바람직하다.In addition, the crystallized mineral in the step (a3) is preferably kaolinite (Kaolinite, Al 2 Si 2 O 5 (OH) 4 ) or mullite (Mullite, 3Al 2 O 3 SiO 2 ).

또한, 상기 (e) 단계 이후, (f) 검수장치(261)에 의한 것으로, MWCNTs의 전기 전도도를 활용한 시멘트 검수 단계를 더 포함하는 것이 바람직하다.In addition, after the step (e), (f) by the inspection device 261, it is preferable to further include a cement inspection step utilizing the electrical conductivity of the MWCNTs.

본 발명에 따른 방법에 따라, 엉킴 및 뭉침 현상이 방지되어, 극초고강도 콘크리트를 생산하거나, 균열발생을 억제할 수 있는 CNT 교착형 혼합시멘트의 제조가 가능하다. 이는, 적절한 용제를 활용한 분산 기법 및 광물 내 결정화 기술이 적용됨으써 가능하다.According to the method according to the present invention, entanglement and agglomeration are prevented, and it is possible to produce ultra-high-strength concrete or to manufacture a CNT-adhesive mixed cement capable of suppressing cracking. This is possible by applying a dispersion technique using an appropriate solvent and a crystallization technique in minerals.

특히, 이러한 방법으로 제조되는 CNT 교착형 혼합시멘트에 의하여, MWCNTs의 우수한 열전도율을 활용하여 중심부의 높은 온도를 표면으로 방열 가능한바, 매스콘크리트의 열안정화가 가능하다. 또한, MWCNTs의 높은 인장강도를 활용, 콘크리트의 낮은 파괴인성을 상쇄하는 균열저항 콘크리트 제조가 가능하다.In particular, by using the CNT interlocking type mixed cement prepared in this way, it is possible to heat the high temperature in the center to the surface by utilizing the excellent thermal conductivity of MWCNTs, thereby enabling heat stability of the mass concrete. In addition, by utilizing the high tensile strength of MWCNTs, it is possible to manufacture crack-resistant concrete that compensates for the low fracture toughness of concrete.

본 발명은 성능은 물론 경제성에서도 우수한 효과를 가져온다. MWCNTs 분산 효과 극대화로 재료의 혼입량이 저감되어 종래 기술 상의 CNTs 혼입량(1∼5wt.%) 대비 1/10~1/30 수준으로 저감이 가능하다. 또한, 이로 인하여 초기 균열 발생 확률이 15%저감된다면, 연간 20억 이상의 사회 경제적 비용절감이 가능하다. The present invention brings an excellent effect not only in performance but also in economic efficiency. By maximizing the dispersion effect of MWCNTs, the amount of mixing of materials is reduced, and it is possible to reduce the level of mixing with CNTs (1 to 5 wt.%) In the prior art to 1/10 to 1/30. In addition, if the probability of the initial crack occurrence is reduced by 15% due to this, it is possible to reduce socio-economic cost by more than 2 billion per year.

한편, MWCNTs의 높은 전기전도성을 활용한 부재 내부의 모니터링 기술의 제공이 가능하다. 즉, 콘크리트 부재를 전도성 물질로 변환하여, 열화 및 균열발생에 관한 건전도 모니터링이 가능하다. 이를 통해, 품질이 낮은 CNT 교착형 혼합시멘트를 검수 단계에서 확인할 수 있어서, 품질 향상 및 균등화에 도움을 줄 수 있다. On the other hand, it is possible to provide a monitoring technology inside the member utilizing the high electrical conductivity of MWCNTs. That is, by converting the concrete member to a conductive material, it is possible to monitor the health of deterioration and cracking. Through this, it is possible to check the low-quality CNT deadlock mixed cement at the inspection stage, which can help in improving and equalizing the quality.

도 1은 종래 기술에서 MWCNTs가 갖는 문제점을 설명하기 위해 촬영한 SEM 마이크로그래피를 도시한다.
도 2는 본 발명에 따른 방법을 설명하기 위한 다이어그램이다.
도 3은 본 발명에 따른 방법에서 환류법 적용을 설명하기 위한 다이어그램이다.
도 4는 본 발명에 따른 방법에서 결정화를 설명하기 위한 다이어그램이다.
도 5는 본 발명에 따른 방법에서 시멘트 매트릭스 내에서 MWCNTs가 크랙을 연결해주는 효과를 설명하기 위한 도면이다.Figure 1 shows a SEM micrograph taken to illustrate the problem of MWCNTs in the prior art.
2 is a diagram for explaining the method according to the present invention.
3 is a diagram for explaining the application of the reflux method in the method according to the present invention.
4 is a diagram for explaining crystallization in the method according to the present invention.
5 is a view for explaining the effect of connecting the MWCNTs cracks in the cement matrix in the method according to the present invention.

이하, 도면을 참조하여 본 발명을 보다 상세히 설명한다. Hereinafter, the present invention will be described in more detail with reference to the drawings.

도 2는 본 발명에 따른 방법을 설명하기 위한 다이어그램이다. 2 is a diagram for explaining the method according to the present invention.

일반적인 시멘트 제조 방법과 달리, MWCNTs 처리부(100)가 부가되어, 원료 사일로(210)에 MWCNTs를 처리하여 시멘트와의 건식 결합을 가능하게 한다. 특히, 일반적인 CNT 결합과 달리, 엉킴 및 뭉침 현상을 방지할 수 있다. Unlike a typical cement manufacturing method, the MWCNTs processing unit 100 is added to process the MWCNTs on the raw material silo 210 to enable dry bonding with cement. In particular, unlike general CNT bonds, it is possible to prevent entanglement and aggregation.

엉킴 및 뭉침 현상의 방지를 위해, 본 발명은 3단계에 걸친 MWCNTs 처리 방법을 제안한다.In order to prevent entanglement and clumping, the present invention proposes a three-step MWCNTs treatment method.

먼저, 제 1 단계로서, MWCNTs 전처리부(110)가 반데르발스 힘을 제거하도록 NMP(N-methyl-2-pyrrolidone) 용제와 레시틴(Lecithin surfactant)을 이용하여 MWCNTs를 전처리한다. First, as a first step, the MWCNTs pre-treatment unit 110 pre-treats the MWCNTs using an NMP (N-methyl-2-pyrrolidone) solvent and lecithin surfactant to remove van der Waals forces.

MWCNTs에서 발생하는 엉킴 및 뭉침 현상은, 나노 규모에서 발생되는 입자들 간의 반데르발스 힘의 작용에 의한 것이다. 본 발명은, 메틸기의 N-methyl-2-pyrrolidone(NMP) 특수 용제 및 레시틴(Lecithin surfactant) 용제를 활용한다. 이를 이용하여, 나노 범위에서의 분산이 가능하며, 반데르발스 힘에 대항해 1년 이상 반영구적으로 분산이 유지될 수 있다.The entanglement and agglomeration phenomenon that occurs in MWCNTs is due to the action of van der Waals forces between particles generated at the nanoscale. The present invention utilizes a methyl group N-methyl-2-pyrrolidone (NMP) special solvent and a lecithin surfactant solvent. Using this, dispersion in the nano-range is possible, and the dispersion can be maintained semi-permanently for more than a year against the van der Waals force.

다음, 제 2 단계로서, MWCNTs 환류적용부(120)가 상기 전처리된 MWCNTs에 환류법을 적용하도록 카르복실기(COOH)를 부여한다.Next, as a second step, the MWCNTs reflux application unit 120 provides a carboxyl group (COOH) to apply the reflux method to the pre-treated MWCNTs.

즉, MWCNTs 입자간 분산 작용을 위한 전처리 후에 MWCNTs와 시멘트 입자간 교착의 용이성을 위하여 MWCNTs 표면에 환류법(reflux)을 적용, 카르복실기(COOH) 구조를 갖는 그룹을 부여한다(도 3 참조). 카르복실기 기능이 부여된 CNTs 입자들은 시멘트의 주된 조성성분 즉, CaO, SiO2, Al2O3 등과 화학적으로 결합이 가능하다(도 4 참조). 결국 시멘트와 MWCNTs가 갖는 각각의 화학적 특성을 바탕으로 시멘트 제조 공정 중 소성 단계 직전에 MWCNTs를 투입함으로써, 시멘트 원재료들의 액상화 및 단계별 화학반응을 유도하여 시멘트 클링커와 MWCNTs 입자의 결속력을 유도하는 것이다. That is, after pre-treatment for the dispersion action between the MWCNTs particles, a reflux method is applied to the surface of the MWCNTs to facilitate the adhesion between the MWCNTs and the cement particles, and a group having a carboxyl group (COOH) structure is given (see FIG. 3). CNTs particles to which the carboxyl group function is imparted can be chemically bonded to the main compositional component of cement, that is, CaO, SiO 2 , Al 2 O 3 and the like (see FIG. 4). Eventually, based on the chemical properties of cement and MWCNTs, MWCNTs are introduced immediately before the firing step in the cement manufacturing process, thereby inducing liquefaction of the raw materials of cement and step-by-step chemical reactions to induce the binding force between cement clinker and MWCNTs particles.

다음, 제 3 단계로서, MWCNTs 결정화부(130)에서 결정화 광물에 상기 카르복실기가 부여된 MWCNTs를 투입한다. Next, as a third step, the MWCNTs crystallization unit 130 injects the MWCNTs to which the carboxyl group is attached to the crystallized mineral.

시멘트의 소성 단계 직전에 직접 투입되는 MWCNTs는 시멘트 원재료들 사이 일부분에 국한되어 교착이 이루어지거나, MWCNTs가 일부 유실될 수 있는 등의 문제점이 발생할 수 있다. 이의 해결방안으로 본 발명에서는 고농도의 MWCNTs 입자를 카올리나이트(Kaolinite, Al2Si2O5(OH)4)나 멀라이트(Mullite, 3Al2O3SiO2)와 같이 시멘트의 원재료 광물에 비해 작은 크기의 광물 내에 결정화(crystallize)시킨다. 이렇게 결정화 된 광물을 시멘트 제조 공정 중 소성 전 단계에 투입할 시, 습식 단계인 시멘트 클링커 내 나노 범위에서의 고른 분포를 나타낼 수 있다. MWCNTs that are directly injected immediately before the calcination step of cement may be confined to a portion between the raw materials of the cement, causing a deadlock, or some loss of MWCNTs. As a solution to this, in the present invention, MWCNTs particles of high concentration are smaller in size than the raw material mineral of cement, such as kaolinite (Al 2 Si 2 O 5 (OH) 4 ) or mullite (Mullite, 3Al 2 O 3 SiO 2 ). Crystallize in the mineral. When the crystallized mineral is added to the pre-firing step in the cement manufacturing process, it can exhibit an even distribution in the nano-range in the wet phase cement clinker.

이와 같은 방식으로, 시멘트에 혼입될 MWCNTs가 MWCNTs 처리부(100)에서 처리되어 준비된다. In this way, MWCNTs to be incorporated into the cement are prepared and processed in the MWCNTs processing unit 100.

한편, 종래 시멘트 제조 방법과 유사하게, 시멘트 원료는 분쇄기(201)에서 분쇄되고, 전기 집진기(202)에서 집진되어 준비된다. On the other hand, similar to the conventional cement manufacturing method, the cement raw material is pulverized in a grinder 201, and is collected and prepared in an electrostatic precipitator 202.

이제, 원료 사일로(210)에는, 먼저 처리된 MWCNTs와 분쇄되고 집진된 시멘트 원료가 유입되어 건식으로 블렌딩된다. Now, to the raw material silo 210, firstly treated MWCNTs and crushed and collected cement raw material are introduced and blended dry.

다음, 블렌딩된 MWCNTs와 시멘트 원료는 예열기(220)에 투입되어 예열되고, 다음 소성기(230)에 투입되어 소성됨으로써 시멘트 클링커가 생성된다. 예열기(220)는 섭씨 850 내지 900도로 예열시킬 수 있다. 소성기(230)는 로터리 킬른(rotary kiln)일 수 있어서 섭씨 1050 내지 1450도에서 소성할 수 있다. Next, the blended MWCNTs and the cement raw material are put into a preheater 220 and preheated, and then injected into a calciner 230 and fired to generate a cement clinker. The preheater 220 may be preheated to 850 to 900 degrees Celsius. The firing machine 230 may be a rotary kiln, so it can be fired at 1050 to 1450 degrees Celsius.

생성된 시멘트 클링커는 클링커 사일로(240)로 이송된다. The resulting cement clinker is transferred to the clinker silo 240.

클링커 사일로(240)에서 이송된 시멘트 클링커에 석고가 추가되며, 이후 분쇄기(250)로 이송된다.Gypsum is added to the cement clinker transferred from the clinker silo 240, and then transferred to the grinder 250.

분쇄기(250)에서는, 석고가 추가된 시멘트 클링커가 분쇄된 후 시멘트 사일로(260)로 이송됨으로써 출하 준비가 완료된다. In the grinder 250, the cement clinker to which the gypsum is added is pulverized and then transferred to the cement silo 260 to prepare for shipment.

이와 같은 방식으로 제조된 CNT 교착형 혼합시멘트는, 나노 규모에서 콘크리트 모체에서 발생한 다양한 균열발생 메커니즘(matrix crack)을 최저 스케일단위에서 제어할 수 있다. 도 5는 시멘트 매트릭스 내에서 MWCNTs가 크랙을 연결해주는 효과(crack-bridging)을 가져올 수 있음을 보여준다.The CNT deadlocked mixed cement manufactured in this way can control a variety of matrix cracks occurring in the concrete matrix at the nanoscale at the smallest scale unit. FIG. 5 shows that MWCNTs in the cement matrix can have a crack-bridging effect.

한편, 본 발명은 별도의 검수장치(261)를 제공한다. 특히, MWCNTs가 높은 전기 전도성을 가지므로, 본 발명에 따른 CNT 교착형 혼합시멘트를 이용한 콘크리트를 전도성 물질로 변환시킨다. 따라서, 전기 전도성을 활용한 다양한 시멘트 검수는 물론 콘크리트 부재의 검수가 가능하다. Meanwhile, the present invention provides a separate inspection device 261. In particular, since MWCNTs have high electrical conductivity, the concrete using the CNT interlaced mixed cement according to the present invention is converted into a conductive material. Therefore, it is possible to inspect various cements as well as inspect concrete members utilizing electrical conductivity.

따라서, 전기 전도성을 활용하는 다양한 방법이 검수장치(261)의 검수 방법으로서 사용될 수 있다. 예를 들어, 라만 분광법, X선 광전자를 활용한 배열 특성 시각화 기법 등이 사용될 수 있다. Therefore, various methods that utilize electrical conductivity can be used as the inspection method of the inspection device 261. For example, Raman spectroscopy, array property visualization techniques using X-ray photoelectrons, and the like can be used.

이상, 본 명세서에는 본 발명을 당업자가 용이하게 이해하고 재현할 수 있도록 도면에 도시한 실시예를 참고로 설명되었으나 이는 예시적인 것에 불과하며, 당업자라면 본 발명의 실시예로부터 다양한 변형 및 균등한 타 실시예가 가능하다는 점을 이해할 것이다. 따라서 본 발명의 보호범위는 특허청구범위에 의해서 정해져야 할 것이다.As described above, the present specification has been described with reference to the embodiments illustrated in the drawings so that those skilled in the art can easily understand and reproduce the present invention, but these are merely exemplary, and those skilled in the art can make various modifications and equivalents from the embodiments of the present invention. It will be understood that embodiments are possible. Therefore, the protection scope of the present invention should be defined by the claims.

100: MWCNTs 처리부
110: MWCNTs 환류적용부
120: MWCNTs 결정화부
201: 분쇄가
202: 전기 집진기
210: 원료 사일로
220: 예열기
230: 소성기
240: 클링커 사일로
250: 분쇄기
260: 시멘트 사일로
261: 검수 장치100: MWCNTs processing unit
110: MWCNTs reflux application unit
120: MWCNTs crystallization unit
201: crushing
202: electrostatic precipitator
210: raw material silo
220: preheater
230: firing machine
240: clinker silo
250: grinder
260: cement silo
261: inspection device

Claims (3)

(a) MWCNTs(Multi-Walled Carbon Nano Tubes) 처리부(100)에서 MWCNTs를 처리하는 단계;
(b) 원료 사일로(210)에서, 상기 처리된 MWCNTs와 시멘트 원료가 블렌딩되는 단계;
(c) 상기 블렌딩된 MWCNTs와 시멘트 원료가 예열기(220)에서 예열되고 소성기(230)에서 소성되어 시멘트 클링커가 생성된 후, 클링커 사일로(240)로 이송되는 단계;
(d) 상기 클링커 사일로(240)에서 상기 시멘트 클링커에 석고가 추가되어 분쇄기(250)로 이송되는 단계; 및
(e) 상기 분쇄기(250)에서, 상기 석고가 추가된 시멘트 클링커가 분쇄된 후 시멘트 사일로(260)로 이송되는 단계를 포함하며,
상기 (a) 단계는
(a1) MWCNTs 전처리부(110)가 반데르발스 힘을 제거하도록 NMP(N-methyl-2-pyrrolidone) 용제와 레시틴(Lecithin surfactant)을 이용하여 MWCNTs를 전처리하는 단계;
(a2) MWCNTs 환류적용부(120)가 상기 전처리된 MWCNTs에 환류법을 적용하도록 카르복실기(COOH)를 부여하는 단계; 및
(a3) MWCNTs 결정화부(130)에서 결정화 광물에 상기 카르복실기가 부여된 MWCNTs를 투입하여, 상기 MWCNTs를 처리하는 단계를 포함하는,
CNT 교착형 혼합시멘트 제조 방법.
(a) processing MWCNTs in a multi-walled carbon nano tubes (MWCNTs) processing unit 100;
(b) in the raw material silo 210, blending the treated MWCNTs with a cement raw material;
(c) the blended MWCNTs and the cement raw material are preheated in a preheater 220 and fired in a calciner 230 to generate a cement clinker, and then transferred to a clinker silo 240;
(d) gypsum is added to the cement clinker in the clinker silo 240 and transferred to the grinder 250; And
(e) in the pulverizer 250, after the cement clinker to which the gypsum is added is crushed, it is transferred to a cement silo 260,
Step (a) is
(a1) pre-treating MWCNTs using N-methyl-2-pyrrolidone (NMP) solvent and lecithin surfactant so that MWCNTs pretreatment unit 110 removes van der Waals forces;
(a2) the MWCNTs reflux application unit 120 applying a carboxyl group (COOH) to apply the reflux method to the pre-treated MWCNTs; And
(a3) MWCNTs crystallization unit 130 comprising the step of injecting the MWCNTs to which the carboxyl group is attached to the crystallized mineral, and processing the MWCNTs,
CNT deadlock mixed cement manufacturing method.
제 1 항에 있어서,
상기 (a3) 단계에서의 상기 결정화 광물은 카올리나이트(Kaolinite, Al2Si2O5(OH)4) 또는 멀라이트(Mullite, 3Al2O3SiO2)인,
CNT 교착형 혼합시멘트 제조 방법.
According to claim 1,
The crystallized mineral in the step (a3) is kaolinite (Kaolinite, Al 2 Si 2 O 5 (OH) 4 ) or mullite (Mullite, 3Al 2 O 3 SiO 2 ),
CNT deadlock mixed cement manufacturing method.
제 1 항에 있어서,
상기 (e) 단계 이후,
(f) 검수장치(261)에 의한 것으로, MWCNTs의 전기 전도도를 활용한 시멘트 검수 단계를 더 포함하는,
CNT 교착형 혼합시멘트 제조 방법.According to claim 1,
After step (e),
(f) by the inspection device 261, further comprising a cement inspection step utilizing the electrical conductivity of the MWCNTs,
CNT deadlock mixed cement manufacturing method.
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Publication number Priority date Publication date Assignee Title
KR20210067832A (en) * 2019-11-29 2021-06-08 단국대학교 산학협력단 Carbon Nanotube Intermixed Cement and preparation method thereof
CN114907075A (en) * 2022-06-02 2022-08-16 浙江大学 High-damping carboxylic styrene-butadiene latex-carbon nanotube cement mortar and preparation method thereof

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KR20120139959A (en) 2011-06-20 2012-12-28 이재환 High density nano coating compositions
JP2013086275A (en) 2011-10-13 2013-05-13 Shimizu Corp Method of manufacturing hardened cement, and hardened cement
KR20130083649A (en) 2012-01-13 2013-07-23 한국과학기술원 Cement compound with carbon nanotube, method for manufacturing the cement mortar, and method for manufacturing cement structure using the cement compound

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KR20120139959A (en) 2011-06-20 2012-12-28 이재환 High density nano coating compositions
JP2013086275A (en) 2011-10-13 2013-05-13 Shimizu Corp Method of manufacturing hardened cement, and hardened cement
KR20130083649A (en) 2012-01-13 2013-07-23 한국과학기술원 Cement compound with carbon nanotube, method for manufacturing the cement mortar, and method for manufacturing cement structure using the cement compound

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210067832A (en) * 2019-11-29 2021-06-08 단국대학교 산학협력단 Carbon Nanotube Intermixed Cement and preparation method thereof
CN114907075A (en) * 2022-06-02 2022-08-16 浙江大学 High-damping carboxylic styrene-butadiene latex-carbon nanotube cement mortar and preparation method thereof

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