Journal of the Mineralogical Society of Korea (한국광물학회지)

The Mineralogical Society of Korea (한국광물학회)
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A Study of Back Transformation of Spinel to Olivine at High Temperature

고온에서 스피넬의 올리빈으로 역상변이 연구

  • Kim Young-Ho (Department of Earth and Environment Science and the Research Institute of Natural Sciences, Gyeongsang National University)
  • 김영호 (경상대학교 지구환경과학과 및 기초과학연구소)
  • Published : 2005.12.01
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Abstract

Results from in-situ high temperature X-ray diffraction measurements show that $Mg_{2}SiO_{4}{-}$spinel converts back to olivine phase only when heated in vacuum, and that at some high temperature, the olivine phase grows with time at the expense of the spinel phase strongly suggesting a 'nucleation and growth' type transition. In order to obtain the activation energy of spinel-olivine back transformation, kinetics measurements were performed on $Mg_{2}SiO_{4}{-}$spinel in vacuum at high temperatures between 1023 and 1116 K. Activation energy was determined using 'time to a given fraction method'. By employing the Avrami equation, it was found that n values generally increase with increasing temperature in a wide range implying that the nucleation and growth mechanism is probably temperature-dependent. It is likely that in spinel, at a relatively lower transformation temperature, after nucleation sites saturated, the growth of the new phase starts on the surface and gradually moves inwards. At high temperatures, however, after nucleation sites saturated, the growth starts both on the surface as well as at the interior.

[ $Mg_{2}SiO_{4}{-}$ ]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 $Mg_{2}SiO_{4}{-}$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 $Mg_{2}SiO_{4}{-}$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.

Keywords

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