A new method is proposed for the calculation of the unrelaxed surface energy of spinel ferrite. The surface energy calculation consists of (1) setting the central and computational domains in the semi-infinite real lattice, having a specific surface, and having an infinite real lattice; (2) calculation of the lattice energies produced by the associated portion of each ion in the relative domain; and (3) dividing the difference between the semi-infinite lattice energy and the infinite lattice energy on the exposed surface area in the central domain. The surface energy was found to converge with a slight expansion of the domain in the real lattice. This method is superior to any other so far reported due to its simple concept and reduced computing burden. The unrelaxed surface energies of the (100), (110), and (111) of ZnFe2O4 and Fe3O4 were evaluated by using in the semi-infinite real lattices containing only one surface. For the normal spinel ZnFe2O4, the(100), which consisted of tetrahedral coordinated Zn2+ was electrostatically the most stable surface. But, for the inverses pinel Fe3O4, the(111), which consisted of tetrahedral coordinated Fe3+and octahedral coordinated Fe2+ was electrostatically the most stable surface.

충남지역 사문암의 기원암인 더나이트와 해즈버자이트로부터의 사문석화작용의 진행 정도는 O'Hanley(1996)의 사문석 조직의 발달단계를 잘 따르고 있다. 사문암내 크롬스피넬의 색은 더나이트내의 것이 갈색 또는 적색이고, 해즈버자이트내의 것은 적색이다. 사문암내 크롬스피넬의 색은 사문석화가 진행될수록 갈색 또는 적색에서 차츰 검은 색이 짙어지고 활석화되면 더욱 검게 변하는데, 이는 변질작용의 진행에 따라 서서히 Fe가 증가하기 때문이다.

The spinel Fe3O4 powders were synthesized using 0.2 M-FeSO4·7H2O and 0.5 M-NaOH by oxidation in air and the spinel LiMn2O4 powders were synthesized at 480 ℃ for 12 h in air by a sol-gel method using manganese acetate and lithium hydroxide as starting materials. The synthesized LiMn2O4 powders were mixed at portion of 5, 10, 15 and 20 wt% of Fe3O4 powders using a ball-mill. The mixed catalysts were dried at room temperature for 24 hrs. The mixed catalysts were reduced by hydrogen gas at 350 ℃ for 2 h. The carbon dioxide decomposition rates of the mixed catalysts were 90% in all the mixed catalysts but the decomposition rate of carbon dioxide was increased with adding LiMn2O4 powders to Fe3O4 powders.

The spinel LiMn2O4 powders were synthesized at 480℃ for 12 h in air by a sol-gel method using manganese acetate and lithium hydroxide as starting material and the Fe3O4 powders were synthesized by the precipitation method using 0.2M-FeSO4·H2O and 0.5M-NaOH. The synthesized Fe3O4 powders were mixed at portion of 5, 10, 15 and 20 wt% about LiMn2O4 powders through ball-milling followed by drying at room temperature for 48 h in air. The mixed catalysts were reduced at 350℃ for 3 h by hydrogen and the decomposition rate of carbon dioxide was measured at 350℃ using the reduced catalysts. As the results of CO2 decomposition experiments, the decomposition rates of carbon dioxide were 85% in all catalysts but the initial decomposition rates of CO2 were slightly high in the case of the 5%-Fe3O4 added catalyst.

[ Mg2SiO4- ]스피넬에서 올리빈으로의 역상변이에 대한 고온 X-선 회절실험 결과, 진공상태에서 가열하였을 때 상변이가 일어나며, 일정한 온도에서 스피넬상으로부터 올리빈상이 시간이 경과하면서 성장하는 것으로 보아 상변이 메커니즘은 '핵생성 및 성장' 형태인 것으로 판단된다. 스피넬 상으로부터 올리빈 상으로 역상변이 할 때의 활성화 에너지를 구하기 위해 Mg2SiO4-스피넬 시료에 대한 상변이 실험을 진공 및 고온(1023∼1116 k)에서 시행하였다. 올리빈 상에 대해 '주어진 시간에 따른 비분율법'을 이용하여 활성화 에너지 값을 결정하였다. 아브라미 방정식을 이용하여 계산한 결과, n값은 대체로 온도가 증가함에 따라 매우 넓은 영역에서 동반 상승하는데, 이러한 현상은 '핵생성 및 성장' 메커니즘이 아마도 온도에 종속적이지 않느냐 하는 것을 제시해주고 있다. 상대적으로 낮은 온도에서는 Mg2SiO4-스피넬은 핵이 생성된 자리가 포화된 후, 새로운 결정상이 표면에서 성장을 시작하고 시간이 지남에 따라 내부 쪽으로 옮아가는 것으로 판단된다. 그러나 고온에서, 성장은 핵이 생성된 자리가 포화되고 난 후 표면뿐만 아니라, 내부에서도 동시에 시작되는 것으로 보인다.