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The defect structure and vacancy distribution in the low-temperature hausmanite

Solid State Ionics
Publication Date
DOI: 10.1016/0167-2738(93)90171-x


Abstract The distribution of Mn 3+ cations and of cationic vacancies different from those in the anhydrous hausmanite, α-Mn 3O 4, has been evidenced in the tetragonal spinel phase obtained by the controlled oxidation of Mn(OH) 2. The single-phase product contains hydroxyl groups in the anionic sublattice and could be defined as hydrohausmanite, α-Mn 3(O, OH) 4. Based on measurements of the integrated intensities of X-ray reflections it has been found that the cationic vacancies in hydrohausmanite are caused mainly by the presence of structural OH - groups. The distribution of vacancies on the tetrahedral and octahedral spinel cationic sublattices may be expressed in the form: Mn 2+ 8−3x+y Mn 3+ 5x 2 −y □ x 2 [ Mn 3+ 16− x 2 □ x 2 ] ( OH) y O 32−y , where x= vacancies/ unit- cell 0643 0642 V 3 and y= hydroxyl groups/ unit- cell.

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