This study investigated the thermal stability of Grubbs' catalyst and its reactivity with self-healing agents for self-healing damage repair. Four types of Grubbs' catalyst supplied by manufacturers were considered and each catalyst was tested in as-received and grinded conditions. Four types of self-healing agents were prepared by varying the mixing ratio of dicyclopentadiene (DCPD) and 5-ethylidene-2-norbonene (ENB). Heat flows as a function of temperature were measured through a differential scanning calorimetry (DSC) to determine the thermal stability of catalysts. Reaction heats of self-healing agents with the catalyst were measured to evaluate the reactivity of the catalyst. For this evaluation, Fluka Chemika Grubbs' catalyst was used based on the maximum temperature and the time to reach the maximum temperature. According to the results, catalysts had different shapes depending on the manufacturer and the results showed that the smaller the size of the catalyst the higher the reactivity with self-healing agents. As the ENB ratio in self-healing agents increased, the maximum temperature increased, and the time to reach the maximum temperature decreased. As the amount of the catalyst increased, the maximum temperature increased, and the time to reach the maximum temperature decreased. Considering the thermal stability of the catalyst and its reactivity with the self-healing agent, combination of 0.5 wt% catalyst and the D3E1 self-healing agent was optimal for self-healing damage repair. Finally, as the thermal decomposition may occur depending on the environmental temperature, the catalyst must not be exposed to temperature higher than that is necessary to maintain the thermal stability of the catalyst.

본 연구에서는 자가손상보수에 적용되는 Grubbs' catalyst의 열안정성과 자가치료제와의 반응성을 조사하였다. 이를 위해 제조사에서 공급된 4종류를 고려하였으며 제조사에서 공급받은 상태와 기계적으로 분쇄시킨 상태로 시험하였다. 자가치료제는 Dicyclopentadiene (DCPD)과 5-ethylidene-2-norbonene (ENB)을 적절한 비율로 혼합한 4종류를 고려하였다. 촉매의 열안정성을 조사하기 위해 시차주사 열량측정장치를 통해 온도에 따른 열흐름 변화를 측정하였다. 자가치료제와의 반응성을 평가하기 위해 촉매와 혼합된 자가치료제의 반응열을 측정하였다. 이때 촉매는 자가치료제와 반응할 때의 최대온도와 최대온도 도달시간을 고려하여 Fluka Chemika Grubbs' catalyst를 적용하였다. 연구결과에 따르면 촉매는 제조사에 따라 다른 형상을 나타내며 입자의 크기가 작은 촉매가 자가치료제와 높은 반응성을 나타내었다. ENB의 혼합비가 높은 자가치료제가 촉매와 혼합되면 최대온도는 증가하고 최대온도 도달시간은 빨라졌다. 또한 촉매의 양이 많을수록 최대온도는 높아지고 최대온도 도달시간은 빨라졌다. 촉매의 열안정성과 자가치료제와의 반응성을 고려할 때 0.5 wt% 촉매와 D3E1 자가치료제가 자가손상보수를 위한 최적 조건임을 알 수 있었다. 마지막으로 노출된 분위기 온도에 따라 촉매에 열분해가 발생할 수 있기 때문에 촉매가 열안정성을 갖는 온도보다 높은 온도에 노출되지 않도록 하여야 한다.

Keywords: Self-healing damage repair, Catalyst, Self-healing agent, Thermal stability, Reaction heat

Keywords: 자가손상보수, 촉매, 자가치료제, 열안정성, 반응열