Gas hydrates are crystalline solids in which gas molecules (guests) are trapped in water cavities (hosts) that are composed of hydrogen-bonded water molecules. During the formation of gas hydrates in seawater, the equilibria and kinetics are then affected by salinity. In this study, the effects of salinity on the equilibria of CO2 and R134-a gas hydrates has been investigated by tracing the changes of operating temperature and pressure. Increasing the salinity by 1.75% led to a drop in the equilibrium temperature of about 2 oC for CO2 gas hydrate and 0.38 oC for R-134a gas hydrate at constant equilibrium pressure; in other words, there were rises in the equilibrium pressure of about 1 bar and 0.25 bar at constant equilibrium temperature, respectively. The kinetics of gas hydrate formation have also been investigated by time-resolved in-situ Raman spectroscopy; the results demonstrate that the increase of salinity delayed the formation of both CO2 and R134-a gas hydrates. Therefore, various ions in seawater can play roles of inhibitors for gas hydrate formation in terms of both equilibrium and kinetics.
콘크리트의 수화물 및 이와 관련된 특성치들은 재령에 따라 변화하며 이는 염화물 확산성과 큰 관련이 있다. 본 연구에서는 세 가지 수준의 물-결합재 비와 플라이 애시 및 고로슬래그 미분말을 30% 혼입한 콘크리트 대하여 2년간 장기 양생을 수행하였다. 5번의 측정 시점(28일, 56일, 180일, 365일, 730일)에 대하여 촉진실험을 통하여 촉진 염화물 확산계수를 평가하였으며, DUCOM을 통하여 도출된 공극률, 염화물 구속능, 투수계수의 변화와 비교하였다. 염화물 확산성과 투수성의 변화 패턴이 가장 유사하였는데, 이는 투수성이 공극률의 제곱에 비례하기 때문이다. 또한, 각 재령 기간 동안 변화하는 비율을 분석하였는데, 초기 재령(재령 28일~56일)에서 공극률, 투수성 및 염화물 확산성의 변화가 지배적이었고, 낮은 물-결합재 비를 가진 OPC 콘크리트에서는 180일까지 확산성의 변화가 지속적으로 크게 평가되었다.
The phenomenon of leaching consists in the dissolution of solid calcium in cement hydrates when concrete is exposed to any aggressive solution. Calcium leaching is completely controlled by the thermodynamic equilibrium between cement hydrates and the porous solution. Thus, it might be described by considering the hydrates (C-S-H and aluminates) solubility evolution with pH. Nevertheless a simplifed model has been proposed considering only the different calcium phases of the hydrates. This study suggested definition of calcium leaching density with type of cement hydrate.
The purpose of this study is to explore the time dependant behaviors of chloride ions adsorption with cement hydrates, focused on its mechanism. AFt phase and CH phase were not able to absorb chloride ion, however, C-S-H phase and AFm phase had a significant chloride adsorption capacity. Based on the results, this study suggested theoretical approach to depict chloride adsorption behavior with elapsed time of C-S-H phase and AFm phase effectively. AFm phase showed a slow chemical adsorption in 40 days, while C-S-H phase showed binding behavior with 3 stages including the stage of instantaneous physical adsorption other stages.
Chloride adsorption is very ambiguous in the mechanisms of deterioration of concrete exposed to marine environment. Author suggested that chloride adsorption with cement hydrates depends on pH value of pore solution. However, adsorbed chloride ions can be dissolved in concrete under the combined deterioration environment of carbonation and chloride penetration. In the condition, the most crucial issue is the amount of dissolved chloride ions in cement paste due to carbonation.
In this study, dynamics experiment was designed to quantify the effect of CaCO3 on chloride adsorption. Based on the experiment results, the final goal of this study is to develop integrated system for predicting chloride adsorption /desorption behaviors.