Introduction to voids in FCC unit cell

In the close packed crystals (FCC, HCP) there are two types of voids tetrahedral and octahedral. OCTAHEDRAL VOIDS IN FCC UNIT CELL The octahedral void has a coordination number 6.The positions of octahedral voids are as follows. 1. BODY CENTER - 1 2. EDGE CENTERS 12 3. NUMBER OF OCTAHEDRAL VOIDS PER UNIT CELL = (12/4)+1 = 4 4. NUMBER OF OCTAHEDRAL VOIDS PER ATOM = 1

FIGURE SHOWING THE VOID AT THE CENTER OF THE BODY SURROUNDED BY SIX ATOMS

FIGURE SHOWING THE VOID AT THE EDGE CENTERS SURROUNDED BY SIX ATOMS

TETRAHEDRAL VOIDS IN FCC UNIT CELL

FIGURE SHOWING EIGHT TETRAGONAL VOIDS SURROUNDED BY FOUR ATOMS POSITION OF OCTAHEDRAL VOIDS: (1/4) th WAY FROM EACH VORTEX / CORNER OF THE CUBE ALONG THE BODY DIAGONAL

SPINEL AND INVERSE SPINEL STRUCTURES OF FERRITE Spinel is an important class of mixed-metal oxides, which has the general chemical composition of AB2O4. Normally A is a divalent metal atom of radius between 80 and 110pm, such as Mg, Fe, Mn, Zn, and Cu and B is a trivalent metal atom of radius between 75 and 90pm, such as Ti, Fe, Al, and Co. There are 8 FCC sub cells. One FCC sub cell has 8 equivalent tetrahedral and 4 octahedral sites. The structure consists of a cubic closed-packed array of 32 oxygen ions, which occupy 64 cubic corners and 48 face centers in one unit cell (containing eight formula units (AB2O4)8). In general totally there are 64 tetrahedral interstitial sites and 32 octahedral interstitial sites available in a spinel ferrite unit cell. But (1/8)th of tetrahedral interstitial sites (8 sites) and half of the total octahedral interstitial sites (16 sites) are occupied. There are two types of sub-cells commonly described for the spinel structure, (i) Structure-A and Structure-B as shown in Figures (1-a) and (1-b) respectively. Structure-A shows the filling of 2 tetrahedral sites within one-eighth of the unit cell and structure-B shows a filled octahedral site. The arrangement of these two cubic sub-cells in one unit cell is shown in Figure 2. In a normal spinel structure, all the 8 divalent cations occupy 8 tetrahedral sites while all the 16 trivalent cations are located in 16 octahedral sites.

FIG.1A

FIG.1B

FIGURE-2

Figure-2 shows an arrangement of structure - A and structure - B in one unit cell. The shaded cube represents structure - A, while white one represents structure - B.Figure-3 shows an example spinel MgAl2O4. Notice the red oxygen atoms, the green magnesium atoms in the tetrahral voids, and the gray aluminum atoms in the octahedral voids. The pattern of structure -A and structure - B can also be seen in Figure 3. Figure-3 shows arrangement of atoms within the MgAl2O4 unit cell. Mg is in green, Al is in gray, and O is in red.

Figure 3

Cobalt ferrite CoFe2O4 has an inverse spinel crystal structure. In general totally there are 64 tetrahedral interstitial sites and 32 octahedral interstitial sites available in an inverse spinel ferrite unit cell like in spinel ferrite unit cell. But (1/8)th of tetrahedral interstitial sites (8 sites) and half of the total octahedral interstitial sites (16 sites) are occupied. In the case of an inverse spinel such as CoFe2O4, the divalent 8 Co cations occupy 8 octahedral coordination sites and 8 Fe3+ cations occupy the other half of the octahedral 8 coordination sites. The remaining 8 Fe3+ cations occupy the 8 tetrahedral coordination sites. The magnetic moments of the octahedral and tetrahedral sites oppose and cancel each other. As in the case of spinel ferrite unit cell oxygen anions occupy 64 cubic corners and 48 face centers in one unit cell (containing eight formula units (AB2O4)8). The crystal structure of CoFe2O4 is shown in Figure 4.

Figure-4 Ferrous ferrite (FeO.Fe2O3) Atomic Number 24

Magnetic moment in Bohr magneton

Ion

Electronic configuration of 3d orbital

Fe 2+

1s2, 2s2 2p6, 3s2 3p6 3d6

Fe 3+

23

1s2, 2s2 2p6, 3s2 3p6 3d5

Composition

Interstitial sites

No. available

No. Occupied 16 (8 Fe 3+, 8 Fe 2+) 8 Fe 3+

FeO.Fe2O3 Inverse spinel

Octahedral Tetrahedral

32 64

Net magnetic moment per sub cell in Bohr magneton 4

The magnetic moment due to 8 Fe 3+ ions in 8 octahedral interstitial sites and 8 Fe ions in 8 tetrahedral interstitial sites oppose and cancel each other. But 8 Fe 2+ ions in 8 octahedral interstitial sites are left in one inverse spinel ferrite unit cell. The number of Fe 2+ ion per FCC sub cell is one. This one Fe 2+ ion gives rise to magnetic moment of 4 Bohr magnetons. The magnetic moment due to 8 Fe 2+ ions in one complete ferrous ferrite inverse spinel unit cell is 32 Bohr magnetons. Materials having inverse spinel ferrite structure are soft ferrite.
3+