Ferrimagnetic Materials and Ferospinel Crystals ( S.O.

Kasap, 1990 - 2001) 1

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FERRIMAGNETIC MATERIALS AND FERROSPINEL

CRYSTALS

Ferrites in Electronic Engineering

Safa Kasap
Department of Electrical Engineering
University of Saskatchewan
Canada

"Unscientific approaches to the construction of models of the world

around us have characterized much of human thinking since the time
immemorial, and they are still widespread. Take, for example, the
version of sympathetic magic based on the idea that similar things
must be connected. It seems natural to many people around the
world that, when in need of rain, they should perform a ceremony in
which water is procured and poured on the ground."

Murray Gell-Mann
(Professor Emeritus, California Institute of Technology; Nobel
Laureate 1969)
The Quark and the Jaguar
(W.H. Freeman and Company,
New York, USA, 1994, p.89)

A magnetic domain of a ferrimagnetic crystal has a net spontaneous magnetization that is due to one array
of atomic magnetic moments all pointing in the same direction and possessing a greater magnitude than
another array of atomic magnetic moments which point in the opposite direction and have a lower
magnitude. Ferrimagnetism is schematically pictured in Figure 1. Typically, ferrimagnetism is found in
materials that have high electrical resistivities and therefore are useful at high frequency magnetic work,
where eddy current losses prevent the use of magnetic metals such as iron.
We can examine the origin of ferrimagnetism in a typical cubic ferrite crystal, for example, in
nickel ferrite, NiFe2O4, which can be written as (NiO)(Fe2O3). In general all similar cubic ferrites have the
chemical composition (MO)(Fe2O3) where M is a divalent transition metal typically, Fe, Mn, Ni, Zn. They
are called spinel ferrites (or ferrospinels) and have soft magnetic properties (easy to magnetize and
demagnetize; narrow B-H curves). The classic example is the iron ferrite (magnetite) which is
(FeO)(Fe2O4) but is simply written Fe3O4.

M
Illustration of magnetic ordering in a
ferrimagnetic crystal. All A–atoms have their
spins aligned in one direction and all B–atoms
have their spins aligned in the opposite direction.
As the magnetic moment of an A–atom is greater
than that of a B–atom, there is net magnetization
M in the crystal.
A B

Figure 1
Ferrimagnetic Materials and Ferospinel Crystals ( S.O. Kasap, 1990 - 2001) 2
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Consider a nickel ferrite crystal. We can write NiFe2O4 as (NiO)(Fe2O4). If we were to show the
ionic charges we would have,
NiFe 2 O 4 = (Ni 2+ O 2 )(Fe3+ 2
2 O3 )

The magnetic properties of nickel ferrite arise from the spin magnetic moments of the metal ions
only, i.e. iron (Fe3+) and nickel (Ni2+) ions. Using Hund's rule, we can work out the number of unpaired
spins in each metal ion.
The Fe atom has the outer electronic structure 3d64s2. The Fe3+ ion therefore has 3d 5. As there are
5 d-orbitals and 5 electrons, all the electrons align their spins (Hund's rule). The net spin magnetic
moment of the Fe3+ ion is 5 Bohr magnetons or 5β as illustrated below:
Fe3+(d5) ↑ ↑ ↑ ↑ ↑ = 5β
The outer structure of the Ni atom is 3d82s2 and that of the Ni2+ ion is 3d 8. Six of the electrons
have to pair their spins so there are 2 unpaired spins and the net spin magnetic moment is 2β.
Ni2+(d8) ↑↓ ↑↓ ↑↓ ↑ ↑ = 2β
The cubic unit cell of the nickel ferrite crystal is shown in Figure 2 where to avoid cluttering we
have not explicitly shown all atoms at all the points. We can consider the structure to be an ionic crystal.
The unit cell has 8 formula units (NiFe2O4) or 56 ions in total. These are 8 Ni2+ ions, 16 Fe3+ ions and 32
O2- ions. All the oxygen ions occupy FCC-like lattice points. For simplicity we can consider the unit cell to
be divided into 8 cubic subcells, each with FCC-like lattice points where there are O2- ions. It appears that
the O2- ions are close-packed. To hold the crystal together, we have to insert the positive metal ions (Ni2+
and Fe3+) between the negative oxygen ions. All the Ni2+ and Fe3+ ions therefore occupy suitable voids, or
interstitial sites, between the O2- ions.

a
a

O2– ions at FCC like sites

Fe3+ at tetrahedral site = +5
Fe3+ at octahedral site = –5
Ni2+ at octahedral site = +2

Subcell

A simplified illustration of the structure of nickel magnetite (NiO)(Fe2O3). This

is the inverse spinel crystal structure. If we replace all the Ni2+ ions with Fe2+
ions, we obtain the iron ferrite (FeO)(Fe2O3).
Figure 2

There are essentially two types of voids, called tetrahedral and octahedral sites, which are available
as identified in Figure 2. A tetrahedral site has 4 neighboring O2- ions which constitute the corners of a
tetrahedron. This site may be occupied by a Fe3+ ion. An octahedral site has 6 neighboring O2- ions which
Ferrimagnetic Materials and Ferospinel Crystals ( S.O. Kasap, 1990 - 2001) 3
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constitute the corners of an octahedron. An octahedral site may be occupied either by a Fe3+ ion or a Ni2+
ion. Only a certain number of these tetrahedral and octahedral sites are occupied as follows:
8 Fe3+ in tetrahedral sites
8 Fe3+ in octahedral sites
8 Ni2+ in octahedral sites
The exchange interactions cause neighboring Fe3+ ions at octahedral and tetrahedral sites to have
opposite spins (like antiferromagnetism), as depicted in Figure 2 for two of them. On the other hand, the
exchange interactions cause the Ni2+ ions at tetrahedral sites to have parallel spins (like ferromagnetism).
Thus the spin magnetic moments of Fe3+ ions at octahedral and tetrahedral sites cancel each other and we
are left with the spin magnetic moments of Ni2+ ions at octahedral sites. The net magnetic moment per unit
cell is then 8 × 2β = 16β per unit cell or 2β per NiFe2O4 molecular unit. The observed experimental value
is 2.3β per NiFe2O4 molecule. The lattice parameter (a) of magnetite is 0.835 nm so that the total magnetic
moment per unit volume neglecting thermal agitation, or the saturation magnetization, Msat, is
Msat = (16β)/a3 = 2.5 × 105 A m-1
so that iron ferrite has Bsat = 0.32 T about 7 times smaller than that of ferromagnetic iron.
The cubic unit cell of NiFe2O4 in Figure 2 is called the inverse spinel. The nickel ferrite,
(NiO)(Fe2O3), iron ferrite, (FeO)(Fe2O3) and cobalt ferrite, (CoO)(Fe2O3), also have the inverse spinel
structure. In the case of iron ferrite (magnetite, Fe3O4), for example, Fe2+ ions replace Ni2+ ions at
octahedral sites. Each Fe2+ ion has a spin magnetic moment of 4β so that magnetite has a saturation
magnetization twice as much as nickel ferrite. Many commercial ferrites are mixtures of various ferrites,
e.g. manganese-zinc ferrite is (MnxZn1–xO)(Fe2O3).

O2– ions at FCC like sites

Zn2+ at tetrahedral site = 0
Fe3+ at octahedral site = –5
Fe3+ at octahedral site = +5
1/ th of cubic unit cell
8

A simplified illustration of the structure of Zn-ferrite (ZnO)(Fe2O3) which has the

normal spinel crystal structure.
Figure 3

Some cubic ferrites, such as the zinc ferrite, (ZnO)(Fe2O3), have a structure that is called the
normal spinel structure rather than the inverse spinel structure. The normal spinel structure is shown in
Figure 3. The difference between normal and inverse spinels is in the types of ions that occupy of
tetrahedral sites (A-sites) and octahedral sites (B-sites) between the O2- ions at FCC-like points (compare
Figure 2 and Figure 3). The positions of Fe3+ and the divalent metal ions are interchanged between the
normal and inverse spinel structures as summarized for the example ferrites, (ZnO)(Fe2O3) and
(NiO)(Fe2O3), in Table 1. Zinc ferrite is non-magnetic but when it is added to nickel ferrite it actually
improves the magnetization of nickel ferrite. Zn2+ ions prefer A-sites, and as three Zn2+ ions substitute for
two Fe3+ ions at A-sites they reduce the number of Fe3+ ions at A-sites. This upsets the antiparallel spin
alignment between Fe3+ ions at A and B sites and hence leads to an increase in the net magnetization. The
improvement occurs up to certain amount of Zn-ferrite and Ni-ferrite mixing, roughly 50%-50% mixing,
as at the extreme end we have 100% Zn-ferrite which is non-magnetic.
Ferrimagnetic Materials and Ferospinel Crystals ( S.O. Kasap, 1990 - 2001) 4
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Ferrites are widely used in HF electronics up to frequencies of several hundred megahertz because
of their high electrical resistivities which lead to negligible eddy current losses.

Table 1
Examples of two cubic ferrites, Zn-ferrite (normal spinel) and Ni-ferrite (inverse spinal).
Ferrite Structure Tetrahedral (A) sites Octahedral (B) sites Net magnetization per
molecular unit
(NiO)(Fe2O3) Inverse spinel 8 × Fe3+ 8 × Fe3+ Ni2+ ion spin = 2β
8 × Ni2+
(ZnO)(Fe2O3) Normal spinel 8 × Zn2+ 8 × Fe3+ Zn2+ ion spin = 0
8 × Fe3+

NOTATION
a lattice parameter
B magnetic field (T)
FCC face-centered cubic crystal structure
H magnetic field intensity (strength) or magnetizing field (A m-1)
HF high frequency
M magnetization vector (A m-1)
M sat saturization magnetization (A m-1)
β Bohr magneton (9.2732 × 10-24 J T-1)

USEFUL DEFINITIONS
Antiferromagnetic materials have crystals in which alternating permanent atomic spin magnetic moments are equal in
magnitude but point in opposite directions (antiparallel) which leads to no net magnetization of the crystal.
Bohr magneton (β) is a useful elementary unit of magnetic moment on the atomic scale. It is equal to the magnetic
moment of one electron spin along an applied magnetic field, β = eh/ 2me.
Ferrimagnetic materials possess crystals that contain two sets of atomic magnetic moments that oppose each other but
one set has greater strength and therefore there is a net magnetization of the crystal. An unmagnetized ferrimagnetic
substance normally has many magnetic domains whose magnetizations add to give no overall magnetization.
However, in a sufficiently strong magnetizing field, the whole ferrimagnetic substance becomes one magnetic
domain with a large magnetization along the field. Some of this magnetization is retained even after the removal of
the field.
Eddy current loss is the Joule energy loss (I2R) in a ferromagnetic material subjected to changing magnetic fields (in ac
fields).The varying magnetic field induces voltages in the ferromagnetic material which drive currents (called eddy
currents) which generates Joule heating due to I2R.
Eddy currents are the induced conduction currents flowing in a ferromagnetic material as a result of varying (ac) magnetic
fields.
Ferrites are ferrimagnetic materials that are ceramics with insulating properties. They are therefore used in HF (high
frequency) applications where eddy current losses are significant. Their general composition is (MO)(Fe2O3) where M
is typically a divalent metal. For magnetically soft ferrites M is typically Fe Mn, Zn, or Ni, whereas for
magnetically hard ferrites M is typically Sr or Ba. Hard ferrites such as BaOFe2O3 have the hexagonal crystal
structure with a high degree of manetocrystalline anisotropy and therefore possess high coercivity (difficult to
demagnetize).
Ferrimagnetic Materials and Ferospinel Crystals ( S.O. Kasap, 1990 - 2001) 5
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Hard magnetic materials characteristically have high remanent magnetizations (Br) and high coercivities (Hc) so that once
magnetized they are difficult to demagnetize. They are suitable for permanent magnet applications. They have broad
B-H hysteresis loops.
Hund's rule states that electrons in a given subshell, nl, try to occupy separate orbitals (different m l) and keep their spins
parallel (same ms). In doing so they achieve a lower energy than pairing their spins (different ms) and occupying the
same orbital (same ml).
Interstitial site (interstice) is an unoccupied space between the atoms (or ions or molecules) in the crystal.
Lattice parameters are the lengths of the sides of the unit cell and the angles between the sides.
Magnetic domain is a region of a ferromagnetic (or ferrimagnetic) crystal which has spontaneous magnetization, i.e.
magnetization in the absence of an applied field, due to the alignment of all magnetic moments.
Magnetization or magnetization vector (M) represents the net magnetic moment per unit volume of material. In the
presence of a magnetic field, individual atomic moments tend to align with the field which results in a net
magnetization.
Soft magnetic materials characteristically have high saturation magnetizations (Bsat) but low saturation magnetizing
fields (Hsat) and low coercivities (Hc) so that they can be magnetized and demagnetized easily. They have tall and
narrow B-H hysteresis loops.

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Last Updated: 10 April 2001
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