Swelling Behavior and Hydration Number of Langmuir-Blodgett Films of Metal-Palmitate Deposited on a Piezoelectric Quartz Crystal Plate

압전수정결정판 위에 적층된 금속-Palmitate Langmuir-Blodgett 막의 팽창거동 및 수화수

Monolayers of calcium palmitate were deposited on a piezoelectric quartz crystal plate by the Langmuir-Blodgett(LB) technique, and it was found from frequency changes of the quartz crystal deposited LB films. The usual carbonyl absorbance at 1704 cm$^{-1}C$ was replaced by the split band in the 1540~1590 cm$^{-1}C$. The two absorptions at 1580 cm$^{-1}C$ and 1540 cm$^{-1}C$ were assigned to the antisymmetric stretching vibration of the calcium carboxylate group and the hydrated species due to the lowering carbonyl stretching frequency by hydrogen bonding$^1$ respectively. Besides, it was demonstrated by X-ray diffraction analysis. The swelling behaviour of LB films in water phase at 23$^{\circ}C$ was observed from the frequency change of the LB films deposited quartz crystal with time. Calcium palmitate LB films has been found to swell substantially in water without flaking, whereas hexadecanol LB films hardly swelled in water. Amount of swelling of calcium palmitate LB films was equivalent to 47 wt.${\%}$ of the dry LB films, which means that ca. 7 water molecules were incorporated per calcium palmitate amphiphile. Chemical structure of calcium palmitate LB film was estimated as [CH$_3$(CH$_2$)$_{14}$COO]$_2$Ca${\cdot}$XH$_2$O, and the hydration number was 1.

Calcium-palmitate의 단분자막을 압전수정결정 위에 Langmuir-Blodgett(LB) 기법으로 적층시켜 수정판의 진동수 변화로부터 LB막의 적층수를 평가할 수 있었다. 바탕용액에 Ca$^{2+}C$ 이온을 포함하는 palmitic acid(PA) 단분자막으로부터 이전 및 적층된 LB막 물질을 적외선 분광분석을 한 결과 1704 cm$^{-1}C$에서 갈라진 흡수띠가 나타나는 것으로 보아 calcium palmitate가 형성되었음을 알 수 있었다. 1580cm$^{-1}C$과 1540cm$^{-1}C$의 두 흡수띠는 각각 calcium carboxylate기의 비대칭 신축진동과 carboxylate가 수화되어 대칭강하된 것으로 확인되었다$^1$. 이사실은 X-선 회절분석에 의해서도 확인되었다. 23$^{\circ}C$ 물 속에서 LB막의 팽윤거동을 LB막이 적층된 수정진동판의 진동수 변화로부터 관측되었다. Calcium palitate LB막은 충분히 팽윤이 되었으나 hexadecanol LB막은 거의 팽윤이 되지 않았다. Calcium palmitate LB막 팽창량은 무게비로 건조 LB막의 47${\%}$였으며 calcium palmitate 단위 분자당 7개의 물분자가 결합되었다. Calcium palmitate 건조 LB막의 화학적 구조는 [CH$_3$(CH$_2$)$_{14}$COO]$_2$Ca${\cdot}$XH$_2$O이고 수화수는 1 H$_2$O였다.