College of Science and Engineering

Institute for Rock Magnetism

4. Domain Theory Here we present the Hitchhiker's
A remarkable property of ferrimagnetic materials is not so much that they Guide to Magnetism written by Bruce
have a spontaneous magnetization, but rather that their magnetization M. Moskowitz for the Environmental
can be influenced by the application of very low magnetic fields. Even the Magnetism Workshop held 5-8 June
earth's field (50 μT) can cause magnetization changes even though the 1991 at the Institute for Rock
interatomic exchange forces responsible for the spontaneous Magnetism. It is a great introduction to
magnetization are equivalent to a field of about 1000 T, almost 100 million rock magnetism and something we
times greater than the earth's field. have encouraged many students new
to the field to read. Below are links to
What allows this to occur is the fact that the sample is actually composed the .html version in several sections
of small regions called magnetic domains, within each of which the local with some links to help you navigate
magnetization is saturated but not necessarily parallel. Domains are small through or jump to certain sections as
(1-100's microns), but much larger than atomic distances. you prefer. We also include a .pdf
version. Both versions can be printed,
The existence of domains is hinted at by the observation that some however, if you print the .html version,
magnetic properties, and in particular, coercivity and remanence vary we recommend to print it in landscape
greatly with grain size. This is best illustrated in the figure below, which mode.
shows the variation of Hc with grain size.
Hitchhiker's Guide to Magnetism
(https://drive.google.com/file/d/15eOq
O9EeiW7rFWQhYLierPna7wcq-
Qvg/view?usp=sharing) in a .pdf
document

More About Hitchhiker's

Guide to Magnetism
1. Definitions and Units (/irm/1-
definitions-and-units)
2. Classes of Magnetic Materials
(/irm/2-classes-magnetic-materials)
3. Magnetic Anisotropy (/irm/3-
magnetic-anisotropy)
The magnetic behavior can be subdivided on the basis of grain size into 5. Thermally Activated
four ranges Magnetizations (/irm/5-thermally-
1. SPM: superparamagnetic activated-magnetizations)
2. SD: single domain 6. Types of Remanence (/irm/6-
3. PSD: pseudo-single domain types-remanence)
4. MD: multidomain 7. References (/irm/7-references)
The maximum coercivity for a given material occurs within its SD range.
For larger grain sizes, coercivity decreases as the grain subdivides into
domains. For smaller grain sizes, coercivity again decreases, but this time
due to the randomizing effects of thermal energy.

Domains constitute a fundamental concept in magnetism. A ferro- or

ferrimagnetic material may be generally defined as one that possesses a
spontaneous magnetization, Ms, dependent on temperature, but only
slightly dependent on applied field. The theory of ferromagnetism, based
on electronic exchange forces, predicts the magnitude of Ms, but says
nothing about the direction of Ms. Experimentally, it is observed that for a
homogeneous specimen at constant temperature, the magnitude of Ms is
uniform but the direction of Ms is in general not uniform from one region
to another (on a scale of microns to millimeters). Uniformity of direction is
attained only by applying a large enough field to drive the domains out of
the sample, or by reducing the particle's dimensions to small enough size
to prevent domain formation.

Domains are formed for the following reason. Consider a large single
crystal.
Suppose it is uniformly magnetized, and hence a single domain. Surface
charges will form on the ends due to the magnetization and are
themselves a second source of a magnetic field (the demagnetizing field).
The energy associated with the surface charge distribution is called the
magnetostatic energy. It is just the volume integral of the field over all
space.

The magnetostatic energy can be approximately halved if the

magnetization splits into two domains magnetized in opposite directions.
This brings (+) and (-) charges closer together, thus decreasing the spatial
extent of the demagnetizing field.

This subdivision into more and more domains can not continue
indefinitely because the transition region between domains (called a
domain wall) requires energy to be produced and maintained. Eventually
an equilibrium number of domains will be reached for a given particle
size.

Domain walls are interfaces between regions in which the magnetization

has different directions. Within the wall, the magnetization must change
direction from that in one domain to that in the other domain. Domain
walls have a finite width that is determined principally by exchange and
magnetocrystalline energy.
Let's consider a domain wall in which the magnetization changes by 180°.
The change in magnetization within the wall can be gradual as in (a) or
abrupt as in (b).

The exchange energy acts to keep spins parallel and can be kept small if
the 180°rotation takes place gradually, over many atomic units. Therefore,
the exchange energy is small in (a) but large in (b).

However, the spins within the wall are no longer aligned along an easy
axis of magnetization. This produces an anisotropy energy, which is high
in (a) but low in (b).

The exchange energy tends to make the wall as wide as possible whereas
the anisotropy tends to make the wall as thin as possible. As a result of
this competition between exchange and anisotropy energies,the domain
wall has a finite width (on the order of 100 nm) and surface energy.

The interplay between long range and short range effects results in the
domain states being grain-size dependent. In addition, the number of
domains for a given grain size depends on the magnitudes of the
exchange, magnetocrystalline, and saturation magnetization. As
mentioned before, these constants are dependent on temperature as well
as composition. Hence domain states in different magnetic minerals
(magnetite and hematite) will have a different grain size dependence. The
domain states will also vary with temperature for a single grain size.
However, as a rule of thumb, the larger the grain size the more domains it
contains.

Single Domain (SD)

As the grain size decreases, a critical size will be reached where the grain
can no longer accommodate a wall. Below this critical size, the grain
contains a single domain (SD). An SD grain is uniformly magnetized to its
saturation magnetization.

SD grains are very important. To change the magnetization of a MD grain,

all you need to do is translate the domain wall, a energetically easy
process, which can be accomplished in relatively low fields. Thus MD
grains are magnetically soft with low values of coercivities and
remanence.
However, the only way to change the magnetization of a SD grain is to
rotate the magnetization, an energetically difficult process. Thus, SD
grains are magnetically hard and have high coercivities and remanence.
Here is an example of an SD and MD grain as characterized by hysteresis
loops:

The critical size for SD behavior depends on several factors including, the
saturation magnetization and the shape of the grain. Most estimates of
the SD-MD transition size are based on theoretical calculations. For
magnetite, the best estimate for the transition size is about 80 nm. Here
are some theoretical results:
For hematite, the transition size from SD to MD is much larger (15 mm),
primarily because the saturation magnetization is about 200 times lower
than for magnetite.

Pseudo-Single Domain (PSD)

The distinction between SD and MD is straightforward. However, small

MD grains exhibit a mixture of SD-like (high remanence) and MD-like (low
coercivity) behavior. For magnetite, this behavior occurs in the size range
between 0.1-20 μm.

There has been much theoretical and experimentally work on PSD grains.
Some current thinking is that small MD particles that contain just a few
domains may actually have difficulty nucleating domains. In some cases
MD grains exist in metastable SD states. The transformation of one
domain state into another, such as addition or loss of domains, is call
transdomain transformation.

The importance of PSD behavior in magnetite, is that the grain size range
for PSD behavior covers the range in sizes that most commonly occur in
natural samples.

Superparamagnetism (SPM)

As particle size continues to decrease within the SD range, another critical

threshold is reached, at which remanence and coercivity go to zero. When
this happens, the grain becomes superparamagnetic.

An SD particle of volume v has a uniform magnetization directed along the

easy axis of magnetization. If v is small enough, or the temperature is high
enough, thermal energy (kT) will be sufficient to overcome the anisotropy
energy separating the (+) and (-) magnetization states and cause a
spontaneous reversal of magnetization.
For superparamagnetic particles, the net magnetic moment in zero field
and at T >0K, will average to zero. In an applied field, there will be a net
statistical alignment of magnetic moments. This is analogous to
paramagnetism, except now the magnetic moment is not that of a single
atom, but to an SD particle containing 105 atoms. Hence, the term
superparamagnetism, which denotes a much higher susceptibility value
than that for simple paramagnetism.

In response to a change in the applied field or temperature, an ensemble

of SPM particles will approach an equilibrium value of magnetization with
a characteristic relaxation time, first derived by Néel:

where

f0 -frequency factor (109sec-1)

Ku -anisotropy constant

v -particle volume

k -Boltzmann constant

T -absolute temperature

The exponential nature of the relaxation time on v and T makes it possible

to define a blocking temperature, TB (at constant volume), or blocking
volume vB, (at constant temperature) at which the magnetization goes
from an unstable condition (t<<t) to a stable condition (t>>t). For example,

t (sec)

21 1
60 1017

In spherically shaped magnetite at room-temperature, this change in

energy corresponds to an increase in size from only 22 to 33 nm!

In nature, fine particles of magnetite can acquire stable remanence as

they pass through the blocking conditions as they cool from high
temperatures or grow authigenically or diagenically at low temperatures.

Initial Susceptibility

Initial susceptibility is measured in a low AC or DC field (<1mT) and is

defined as the ratio of M/H. Initial susceptibility is due to reversible
displacements of mobile domain walls in MD particles or moment rotation
in SD particles. In the latter case, low fields are not very effective in
rotating SD moments. Therefore, susceptibilities in SD and PSD grains are
usually lower than that of MD grains.
However, what is actually measured in the laboratory is the apparent
susceptibility, χo, not the intrinsic susceptibility, χi. The difference is due to
the effects of self-demagnetization.

Remember, inside a grain, the applied field, H, is modified by the

demagnetizing field resulting from surface charges. The magnitude of the
demagnetizing field is NM. Inside a grain, the internal field is

Hi = H-NM

M =χiHi

The observed susceptibility is the ratio of M to the applied field

For strongly magnetic materials, like magnetite

Nχi > 1

χo » 1/N

N is weakly related to grain shape and domain state. It is usually assumed

to be a constant, independent of grain size. If this is so, low-field
susceptibility can be used as a reliable measure of magnetite content.

A small fraction of SPM particles can contribute significantly to the room-

temperature susceptibility of SD or MD grains. Calculations show SPM
susceptibility can be 10-100 times that of an equivalent amount of SD
grains.

Frequency Dependence of Susceptibility

Low-field susceptibility can also be measured at different frequencies of

the applied AC field. SPM grains show the most pronounced frequency
dependence of low-field susceptibility. Changing the measurement
frequency is basically changing the amount of time allowed for the grains
to react to a change in applied field. This is the same as changing the
blocking volumes. As the frequency of the measurement increases, the
SPM/SD boundary shifts to smaller volumes and more grains become
blocked.

Experimental results show that the % decrease in χo per decade of

frequency is:

1-20% SPM grains

<1% SD,MD grains
Hysteresis Properties of SD, PSD, and MD Particles

The shape of a hysteresis loop is determined partly by the domain state.

Loops for SD materials are typically wider than loops for MD materials.
This is just a reflection of the higher coercivity and remanence in SD
material. The hysteresis loop parameters, Mr/Ms and Hr/Hc>, have proven
very useful in distinguishing domain state. In fact, Mr/Ms is a definitive
test for differentiating between SD and non-SD particles. Here are results
for magnetite:

SD Hysteresis Properties

For an assembly of SD grains with randomly oriented easy axes, Mr/Ms

can be calculated and depends on the type of anisotropy:

Type of Anisotropy Mr/Ms Source

uniaxial 0.5 shape,stress
magnetocrystalline (cubic)
 Type of Anisotropy Mr/Ms Source
K1 < 0 0.87 intrinsic
K1 > 0 0.83 intrinsic

Hc > 10-15 mT for equidimensional particles

Hc > 30-40 mT for acicular particles

Hr/Hc = 1-2

MD and PSD Hysteresis Properties

For an assembly of MD or PSD particles, it is more difficult to calculate

Mr/Ms and Hr/Hc ratios. From models based on displacements of mobile
domain walls and experimental results on synthetic samples, the
following values are typical:

Parameter PSD MD
Mr/Ms 0.1-0.5 <0.1
Hr/Hc 2-4 >4
Hc 10-15 mT <10 mT

SPM Hysteresis Properties

SPM particles exhibit no remanence or coercivity. The shape of the

hysteresis loop is thus extremely thin. SPM grains show a very steep initial
rise in magnetization with field and then a more gradual increase to
saturation. However, in a mixture of mostly SPM grains but with some SD
or MD grains, typical values for hysteresis parameters are:

Mr/Ms << 0.01

Hr/Hc > 10

Separation of SPM from MD grains based on hysteresis properties can be

a problem using just room temperature measurements. In some cases,
cooling the sample down to very low temperatures can be helpful.
Grains that are SPM at room temperature can become blocked and SD at
low temperatures. Significant changes in hysteresis parameters between
room temperature and 77K is diagnostic of a SPM contribution.

Summary

As shown above, the Mr/Ms -Hr/Hc diagram is a useful indicator of

domain states
Mixtures of Domain States

Often, natural samples may contain two populations of grain sizes, a

coarse MD fraction and a fine SD fraction. This makes the interpretation
of hysteresis data more complicated. For example, Hr/Hc is biased toward
the low-coercivity fraction, as shown here

Very high values of this ratio indicates SPM particles.