• Corrosion Science and Technology
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• 제8권2호
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• pp.81-88
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• 2009

Chloride induced corrosion of steel reinforcement inside concrete is a major concern for concrete structures exposed to a marine environment. It is well known that transport of chloride ions in concrete occurs mainly through ionic/molecular diffusion, as a gradient of chloride concentration in the concrete pore solution is set. In the process of chloride transport, a portion of chlorides are bound in cement matrix then to be removed in the pore solution, and thus only the rest of chlorides which are not bound (i.e. free chlorides) leads the ingress of chlorides. However, since the measurement of free/bound chloride content is much susceptible to environmental conditions, chloride profiles expressed in total chlorides are evaluated to use in many studies In this study, the capacity of chloride binding in cement matrix was monitored for 150 days and then quantified using the Langmuir isotherm to determine the portions of free chlorides and bound chlorides at given total chlorides and the redistribution of free chlorides. Then, the diffusion of chloride ion in concrete was modeled by considering the binding capacity for the prediction of chloride profiles with the redistribution. The predicted chloride profiles were compared to those obtained from conventional model. It was found that the prediction of chloride profiles obtained by the model has shown slower diffusion than those by the conventional ones. This reflects that the prediction by total chloride may overestimate the ingress of chlorides by neglecting the redistribution of free chlorides caused by the binding capacity of cement matrix. From the evaluation, it is also shown that the service life prediction using the free chloride redistribution model needs different expression for the chloride threshold level which is expressed by the total chlorides in the conventional diffusion model.

• 한국콘크리트학회:학술대회논문집
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• 한국콘크리트학회 2006년도 추계 학술발표회 논문집
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• pp.537-540
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• 2006

Over the past few decades, a considerable number of studies on the durability of concrete have been carried out extensively. A lot of improvements have been achieved especially in modeling of ionic flows. However, the majority of these researches have not dealt with the chloride binding isotherm based on the mechanism, although chloride binding capacity can significantly impact on the total service life of concrete under marine environment. The purpose of this study is to develop the model of chloride binding isotherm based on the individual mechanism. It is well known that chlorides ions in concrete can be present; free chlorides dissolved in the pore solution, chemical bound chlorides reacted with the hydration compounds of cement, and physical bound attracted to the surface of C-S-H grains. First, sub-model for water soluble chloride content is suggested as a function of pore solution and degree of saturation. Second, chemical model is suggested separately to estimate the response of binding capacity due to C-S-H and Friedel's salt. Finally, physical bound chloride content is estimated to consider a surface area of C-S-H nano-grains and the distance limited by the Van der Waals force. The new model of chloride binding isotherm suggested in this study is based on their intrinsic binding mechanisms and hydration reaction of concrete. Accordingly, it is possible to characterize chloride binding isotherm at the arbitrary stage of hydration time and arbitrary location from the surface of concrete. Comparative study with experimental data of published literature is accomplished to validity this model.

• 분석과학
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• 제25권1호
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• pp.33-38
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• 2012

염화물 고정화능력의 중요성에도 불구하고 고정화능력을 측정하는 것은 어려우며 특히, 이미 건설되어 공용중인 구조물에서는 더욱 어렵다. 실제로 고정염화물을 측정하는 과정은 온도, 시료의 분말도, 공극수 추출기법 등과 같은 환경적 요인에 의해 큰 영향을 받는다. 본 연구에서는 X-선 회절분석법(XRD; X-ray diffraction)을 이용하여 콘크리트 내 염화물 이온의 고정화능력을 정량화하는 방법에 대해 중점을 두고 연구를 진행하였다. 염화물의 고정능력 isotherm은 물/시멘트비, 양생기간, 결합재 종류에 영향을 받으며 Langmuir isotherm 을 통하여 일단 결정된 고정염화물(Friedel 염)은 XRD를 이용하여 동시에 분석을 진행한다. XRD 그래프에서 나타난 고정염화물량의 피크 강도와 측정된 고정염화물의 총량의 관계를 결정한다. 결과적으로 양생기간이 증가될수록, 물/시멘트비가 감소될수록 고정화 능력은 증가하였다.

• 한국콘크리트학회:학술대회논문집
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• 한국콘크리트학회 1999년도 학회창립 10주년 기념 1999년도 가을 학술발표회 논문집
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• pp.131-134
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• 1999

Microstructure modification and electrochemical properties are investigate to estimate the effects of internal chlorides on the steel corrosion in the blended cement systems. According to the test results, slag cement system showed high chloride binding capacity and low corrosion rate. The impedance data showed three distince arcs from lowest(mHz) frequency to highest (MHz) frequency due to product layer, interfacial reaction and bulk matrix. Through the microstructural investigation, fine steel-matrix interface of slag cement system was observed but rough steel-matrix interface of OPC system was observed. Friedel's salt was thought that the substantial material contributed to the chloride binding of slag cement system.

• 대한토목학회논문집
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• 제28권5A호
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• pp.709-718
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• 2008

본 논문에서는 온도 및 습도 등 환경조건의 변화와 염소이온의 확산, 이송 및 구속 현상을 고려하는 콘크리트 내부로의 염소이온 침투해석 프로그램을 개발하였다. 외부 환경조건의 변화를 고려하기 위하여 온도와 습도분포 해석을 동시에 수행할 수 있도록 하고, 확산계수의 온도, 습도 및 재령에 대한 변동성을 반영하였다. 실측데이터와의 비교를 통해 개발된 프로그램이 실측결과와 잘 일치함을 검증하였으며, 건습의 반복 등 외부 환경조건의 변화에 따라 콘크리트 내부 수분량이 변화하는 경우 염소이온이 표면부에 축적되는 현상의 기본 메커니즘과 그에 따른 철근부식 발생의 촉진과정을 예제해석을 통해 규명하였다.

• 대한화학회지
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• 제20권5호
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• pp.406-416
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• 1976

Pyridine관여 탈수소 효소는 $N^1$-alkylnicotinamide chloride 유도체에 의하여 저해 작용을 받고 있는 바 저해제이 농도 변화에 따른 효소 저해작용이 가역 또는 비가역 불활성화 반응에 기인하는지의 여부를 밝혀 보기 위하여 토끼 근육으로 부터 유리한 L-${\alpha}$-glycerophosphate dehydrogenase를 사용하여 연구하였다. 이 효소의 저해작용은 상용한 저해제 유도체의 농도가 희박했을 경우 가역적인 효소저해 반응을 보여주고 있으나 저해제의 농도가 증가함에 따라 점차 비가역적인 효소 불활성화로서 나타남을 알았으며 이러한 비가역 불활성화 반응은 저해제의 농도가 증가함에 따라 형성될 수 있는 micelle 구조의 미세분자와의 결합에 의한 효소의 변성에 기인할 것이라고 결론을 얻었다.

• Computers and Concrete
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• 제17권1호
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• pp.53-66
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• 2016

Currently, most of the investigations on chloride diffusion were based on the experiments and simulations concerning single cation type chlorides. Chloride diffusion associated with dual or multi cation types was rarely studied. In this paper, several groups of diffusion experiments are conducted using chloride solutions containing single, dual and multi cation types. A multi-ionic model is also proposed to simulate the chloride diffusion behavior in the experimental tests. The MATLAB software is used to numerically solve the nonlinear PDEs in the multi-ionic model. The experimental and simulated results show that the chloride diffusion behavior associated with different cation types is significantly different. When the single cation type chlorides are adopted, it is found that the bound rates of chloride ions combined with divalent cations are greater than those combined with monovalent cations. When the dual/multi cation type chlorides are adopted, the chloride bound rates increase with the $Ca^{2+}/Mg^{2+}$ percentage in the source solutions. This evidence indicates that the divalent cations would markedly enhance the chloride binding capacity and reduce the chloride diffusivity. Moreover, on the basis of the analysis, it is also found that the complicated cation types in source solutions are beneficial to reducing the chloride diffusivity.

• Corrosion Science and Technology
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• 제8권5호
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• pp.171-176
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• 2009

The chloride threshold level (CTL) in mixed concrete containing, ordinary Portland cement (OPC), pulverized fuel ash (PFA) ground granulated blast furnace slag (GGBS), and silica fume (SF) is important for study on corrosion of reinforced concrete structures. The CTL is defined as a critical content of chloride at the steel depth of the steel which causes the breakdown of the passive film. The criterion of the CTL represented by total chloride content has been used due to convenience and practicality. In order to demonstrate a relationship between the CTL by total chloride content and the CTL by free chloride content, corrosion test and chloride binding capacity test were carried out. In corrosion test, Mortar specimens were cast using OPC, PFA, GGBS and SF, chlorides were admixed ranging 0.0, 0.2, 0.4, 0.8, 1.0, 1.5, 2.0, 2.5 and 3.0% by weight of binder. All specimens were cured 28 days, and then the corrosion rate was measured by the Tafel's extrapolation method. In chloride binding capacity, paste specimens were casting using OPC, PFA, GGBS and SF, chlorides were admixed ranging 0.1, 0.2, 0.3, 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0% by weight of binders. At 28days, solution mixed with the powder of ground specimens was used to measure binding capacity. All specimens of both experiments were wrapped in polythene film to avoid leaching out of chloride and hydroxyl ions. As a result, the CTL by total chloride content ranged from 0.36-1.44% by weight of binders and the CTL by free chloride content ranged from 0.14-0.96%. Accordingly, the difference was ranging, from 0.22 to 0.48% by weight of binder. The order of difference for binder is OPC > 10% SF > 30% PFA > 60% GGBS.

• 한국콘크리트학회:학술대회논문집
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• 한국콘크리트학회 2005년도 봄학술 발표회 논문집(II)
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• pp.205-208
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• 2005

The present study surveys the concrete properties-concerned factors influencing the chloride threshold level for steel corrosion in concrete, altogether with supporting experimental works, in particular, chloride binding capacity, buffering capacity, condition of steel-concrete interface and cement replacement. It concluded that the order of the dominance on CTL is such that chloride binding < buffering capacity of cement matrix < physical condition of steel-concrete interface. This is attributed to the fact that calcium hydroxide does not form a continuous layer on the steel surface and that bound chlorides are released at the stage of corrosion initiation.

• 한국구조물진단유지관리공학회 논문집
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• 제12권5호
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• pp.133-142
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• 2008

본 연구에서는 보통포틀랜드시멘트(OPC: ordinary Portland cement), 플라이애쉬(PFA: pulverised fly ash), 고로슬래그미분말(GGBFS: ground granulated blast furnace slag), 실리카퓸(SF: Silica fume)등의 각종 결합재를 적용한 시멘트 페이스트의 염소이온 고정화능력에 관하여 연구하였다. 각각의 사용 시멘트 페이스트는 40%의 물/결합재로 PFA, GGBFS 및 SF 혼화제의 각기 다른 치환률을 갖도록 하였으며 미리 혼합수내에 결합재 중량당 0.1~0.3%의 염소이온을 배합수내에 혼입 포함시켜 배합되어 제조되었다. 염소이온의 측정은 7일간 양생 후 수분 추출 방법을 이용하여 측정하였다. 실험을 통해 염소이온 고정화 능력이 결합재 종류 및 치환률에 의존하고 있음을 확인하였고, 총 염소이온량의 증가는 염소이온 고정화능력을 제한하여 결론적으로 염소이온 고정화를 감소시키고 있음을 보였다. 본 연구에서 최대 30%의 치환율을 가진 PFA와 60%의 치환률을 가진 GGBFS의 경우는 OPC보다 염소이온고정화 능력이 작았으며, SF의 치환률의 증가는 고정화를 감소시키고 있음을 확인하였으며, 이는 포졸란계 재료의 잠재 수화반응 혹은 공극수의 pH 저하등의 이유로 판단된다. 재령 7일에서의 염소이온의 고정화능력은 염해부식에 대한 저항성으로 나타내어지며, 염분을 혼입한 경우의 고정화능력의 순서는 30%PFA > 10%SF > 60%GGBFS > OPC로 나타났다. 더욱이 염소이온의 고정화 거동은 Langmuir isotherm 및 Freundlich isotherm으로 잘 표현될 수 있음을 보였다.