Chapter - 2

Crystal Structure,
Preparation techniques
and
Swift heavy ions irradiation

2.1 Crystal structure of ferrites

Table 2.1 represents types of ferrites with their crystal structure, general
formula and replacements.
Table 2.1 Various Ferrites with their structures and general formula

Sr.
No.

Types

Crystal
structure

General
formula

Replacements

Spinel

Cubic

AIIFe2O4

AII - Mn, Zn, Ni, Mg, Co

Garnet

Cubic

LnIII3Fe5O12

LnIII - Y, Sm, Eu, Gd, Tb,

Dy, Ho, Er, Tm and Lu

Ortho ferrite

Perovskite

LnIIIFeO3

LnIII - Y, Sm, Eu, Gd, Tb,

Dy, Ho, Er, Tm and Lu

Magnetoplumbite

Hexagonal

AIIFe12O19

AII - Ba, Sr, Pb

2.1.1 Spinel ferrite

Spinel ferrite crystallizes in the cubic structure. The spinel lattice is composed
of a close-packed oxygen anions arrangement in which 32 oxygen ions form the unit
cell (the smallest repeating unit in the crystal network). These anions are packed in a
face centred cubic (FCC) arrangement leaving two kinds of spaces between anions:
tetrahedrally coordinated sites (A), surrounded by four nearest oxygen atoms, and
octahedrally coordinated sites (B), surrounded by six nearest neighbour oxygen atoms
(Figure 2.1). There are total 64 tetrahedral sites and 32 octahedral sites in the unit
cell, of which only 8 tetrahedral sites and 16 octahedral sites are occupied, resulting in
a structure that is electrically neutral [1].
Spinels have general formula M(Fe2O4), where M is usually a divalent cation
such as manganese (Mn2+), nickel (Ni2+), cobalt (Co2+), zinc (Zn2+), copper (Cu2+), or
magnesium (Mg2+). M can also represent the monovalent lithium cation (Li+) or even
vacancies, as long as these absences of positive charge are compensated for by
additional trivalent iron cations (Fe3+). The ionic distribution in this kind of structure
may be represented by [MFe1-]A[M1-Fe1+]BO4, where is the inversion parameter
and = 0 and 1 stand for the inverse and normal cases respectively.

- 14 -

Figure 2.1 (a) Spinel structure, (b) octahedral interstice (B site: 32 per unit cell,
16 occupied), and (c) tetrahedral interstice (A site: 64 per unit cell, 8 occupied)

Figure 2.2 Spinel unit cell structure

Although most spinel ferrites are cubic, there are some exceptions like
CuFe2O4 that can have tetragonal unit cell symmetry if the sample is slowly cooled
from high temperatures. There exists a super exchange interaction between the cations
occupied in different interstitial sites through oxygen anion.

2.1.2 Garnet structure

The garnets have orthorhombic crystal structure (oxygen polyhedra,
surrounding the cations) but with trivalent cations (including rare earth and Fe3+)
occupying tetrahedral (d), octahedral (a), or dodecahedrala 12-sided distorted
polyhedral(c) sites. Specifically, the interaction between tetrahedral and octahedral
sites is antiparallel, and the net magnetic moment is antiparallel to the rare earth ions
- 15 -

on the c sites. The garnet structure is one of the most complicated crystal structures
and it is difficult to draw a two dimensional representation that shows clearly all the
ions (160) in the unit cell. For simplicity, only an octant of a garnet structure that
shows just the cation positions is shown in Figure 2.3. The garnet structure is
composed of a combination of octahedral (trivalent cation surrounded by six oxygen
ions), tetrahedral (trivalent cations surrounded by four oxygen ions), and 12-sided
polyhedral - dodecahedral - (trivalent cations surrounded by 8 oxygen atoms) sites,
the orientations of which are shown in Figure 2.4 (a) [2]. The chemical formula for
garnets is 3Me2O35Fe2O3 where Me represents the trivalent rare earth ions like non
magnetic yttrium or a magnetic rare earth such as from lanthanum through ytterbium.

Figure 2.3 Schematic representation of an octant of a garnet crystal structure

(lattice constant a) showing cation positions
(a)

(b)

Figure 2.4 (a) An octant of a garnet crystal structure (b) Unit cell of a rare earth garnet

- 16 -

Figure 2.4 (b) shows a unit cell of rare earth garnet. In YIG, the five iron (III)
ions occupy two octahedral and three tetrahedral sites, with the yttrium (III) ions
coordinated by eight oxygen ions in an irregular cube. The iron ions in the two
coordination sites exhibit different spins, resulting in magnetic behavior. By
substituting specific sites with rare earth elements, interesting magnetic properties can
be obtained. Trivalent iron ions on Tetrahedral (d) and Octahedral (a) are important
for magnetic property. These two sites are coupled anti-ferromagnetically [3] and
yields a Ferrimagnetic crystal [4].

2.1.3 Ortho ferrite structure

Rare earth orthoferrites are classified as ferrites, although they are canted
antiferromagnets. The magnetic oxides with perovskite structure, which have been
studied by Jonker and Van Santen [5], are an exception in the group of oxides. The
perovskite structure is shown schematically in Figure 2.5. Large divalent or trivalent
ions (A) occupy the corners of a cube and small trivalent or tetravalent metal ions (B)
occupy the centre of the cube. The oxygen ions are situated centrally on the faces of
the cube. The general chemical formula is ABO3, where A represents yttrium or a rare
earth.

Figure 2.5 A Perovskite structure of an orthoferrite

The magnetic structure inside of a sublattice is usually collinear

ferromagnetic, but the different sublattices are coupled antiferromagnetically. Due to

- 17 -

the different number of magnetic ions in different sublattices, there is a net resulting
magnetic moment, giving rise to ferrimagnetism. The nature of the superexchange
interaction depends not only on the type of the magnetic ion, but rather strongly on
the bond length and bonding angle. This makes it possible
possible to change the strength and
type of the superexchange interaction.
interaction

2.1.4 Hexagonal Ferrites

Hexaferrite possesses a "magnetoplumbite" structure. The
he symmetry of the
magnetoplumbite structure is hexagonal. Thus, it has a major preferred axis called the
c-axis
axis and a minor axis called the a-axis.
axis. The preferred direction is used to good
advantage as a permanent magnet material. The oxygen ions are closely
clos
packed as
they are in the spinel structure but there are oxygen layers which now include the
Ba2+, Sr2+ or Pb2+ ions which have about the same ionic radii as the oxygen ions and
therefore can replace them in the lattice. Several related ferromagnetic oxides
o
are also
available all of which can be derived by combining the ferrite spinel (MeOFe2O3)
and ferroxdure (BaO6Fe2O3) using the chemical composition diagram shown in
Figure 2.6. The same with chemical formula for each type, namely M, Y, W, Z, X,
and U, is given in Table 2.2 [6].

Figure 2.6 Chemical compositional BaO-MeO-Fe

BaO
2O3 ternary phase diagram showing how the
different hexagonal ferrites are derived

- 18 -

Table 2.2 Hexaferrite types with their chemical formulae, composition and stacking order

Sr.
No.

Hexaferrite
Type

S-Spinel

Composition

Stacking order#

2 MeO2 Fe2O3

BaO6 Fe2O3

RSR*S*

2 BaO2 MeO6 Fe2O3

TSTST

BaO2 MeO8 Fe2O3

RSSR*S*S*

3 BaO2 MeO12 Fe2O3

RSTSR*S*T*S*

2 BaO2 MeO14 Fe2O3

RSR*S*S*

4 BaO2 MeO18 Fe2O3

RSR*S*T*S*

Sub-units for stacking order, using, S = Fe6O8 (spinel), R = BaFe6O11 (hexagonal), and

T = Ba2Fe8O14 (hexagonal). The asterix (*) indicates that the corresponding sub-unit is rotated
180 around the hexagonal axis.

(i) M-type hexaferrite: Magnetoplumbite-structured ferrites having a generic formula

MO6Fe2O3, where M represents a divalent ions such as Ba2+, Sr2+, or Pb2+. It has
hexagonal structure composed of stacked spinel ionic layers with interspaced ionic
layers of M2+, O2- , and Fe. These types of oxide ferrites have extensive magnetocrystalline anisotropy due to their low crystal symmetry. The magnetoplumbite unit
cell contains a total of ten layers, two of which contain the Ba2+: four layers of four
oxygen ions each; followed by a layer of three oxygen ions and one Ba2+ ion; again
followed by four layers of four oxygen as having ions each; and another layer
containing three oxygen and one Ba2+ ion but situated diametrically opposite to the
Ba2+ ion in the previous layer containing Ba2+. The Fe3+ ions are located in the
interstices of these ten layers. There are octahedral and tetrahedral sites plus one more
type not found in the spinel structure in which the metal ion is surrounded by 5
oxygen ions forming a trigonal bi- pyramid in the same layer as the Ba2+ ion.
Figure 2.7 (a) shows the schematic crystal structure of M-type hexaferrites
SrFe12O19/ BaFe12O19. The M-type ferrite crystallizes in a hexagonal structure with 64
ions per unit cell on 11 different symmetry sites (P63/mmc space group). The structure
of M-type hexagonal is stacked alternatively by spinel (S = Fe6O82+) and hexagonal
(R = MFe6O112-) layers. The O2- ions exist as close-packed layers, with M2+
- 19 -

substituting for an O2- in the hexagonal layer. The three parallel (2a, 12k and 2b) and
two antiparallel (4f1 and 4f2) sub-lattices, which are coupled by superexchange
interactions through the O2- ions, form the ferrimagnetic structure [7]. A schematic Mtype structural representation and the surroundings of five Fe3+ sites are shown in
Figure 2.7 (b) by Collomb et al. [8].

Sr2+/ Ba2+

(a)

(b)

Figure 2.7 (a) The crystal structure of M-type hexagonal and (b) BaFe12O19 along with five
Fe sites with their surroundings.

The 24 Fe3+ atoms are distributed over five distinct sites: three octahedral sites
(12k, 2a and 4f2), one tetrahedral (4f1) site and one hexahedral (trigonal bipyramidal)
site (2b).The arrows on Fe ions represent the direction of spin polarization. The unit
cell contains a total of 38 O2- ions, 2 Sr2+ ions, and 24 Fe3+ ions. Fe3+ ions in 12k, 2a,
and 2b sites (16 total per unit cell) have their spins up, while the Fe3+ ions in 4f1 and
4f2 sites (8 total per unit cell) have their spins down, which results in a net total of 8
spins up, and therefore, a total moment of 8 x 5 B = 40 B per unit cell that contains

- 20 -

two Sr2+ ions. The asterix (*) indicates that the corresponding sub-unit is rotated 180
around the hexagonal axis.
Strontium ferrite is almost identical to BaFe12O19 in its crystallographic
structure and magnetic properties, except that the sintered magnets generally have
higher coercivity. The magnetic moments of the iron ions (Fe3+) which lie along the caxis are coupled to each other by a superexchange interaction. The angle between the
ferric cations and oxygen in Fe-O-Fe bonds determines their antiferromagnetism (i.e.,
larger exchange for larger angles). The ferromagnetic resonance (FMR) line width for
a single crystal is reported to range from 10 to 20 Oe [9].

(a)

(b)

Figure 2.8 (a) Y-type hexaferrite structure and (b) A polyhedral representation of the
SrZnCoFe16O27 W-type hexagonal ferrite. Me1 Me7 denote the different polyhedra.

- 21 -

(ii) Y-type hexaferrite: The Me2Y (Y-type) hexaferrite contains different

combination of barium layers and spinel blocks. The unit cell is composed of the
sequence STSTST including three formula units. In Y-type structure, tetrahedral and
octahedral sites are occupied by metal ions. However, the Me2Y has a preferred plane
which is perpendicular to the c-axis in which the magnetization can move freely so
Me2Y hexaferrites cannot be used as a permanent magnet. Figure 2.9 (b) shows the
unit cell cross-section of Y-type hexaferrite and Figure 2.8 (a) represents the
polyhedra of Y-type.
(iii) W-Type hexaferrite: The Me2W (W-type) hexaferrite exhibits a magnetic
uniaxial anisotropy along the c-axis of the hexagonal structure as in the case of the Mtype hexaferrite. The unit cell of W-type composed of the sequence RSSR*S*S*.
There is a 180 rotation between R-R* and S-S* blocks around c-axis. The W
structure consists of one Ba containing layer for every seventh oxygen layer of the
spinel structure and is thus closely related to the M structure. Substitution of different
combinations of divalent metal ions paves the way for changing the saturation
magnetization and Nel temperature of the W hexaferrite. Figure 2.8 (b) shows
polyhedral representation of W-type hexaferrite.
(iv) Z-type hexaferrite: Me2Z (Z-type) being the sum of M and Y compounds, it is
somewhat different in that the M portion attempts to cause a preferential direction
along the c-axis while the Y portion attempts to cause planar anisotropy in the plane
perpendicular to the c-axis. The slightly larger uniaxial anisotropy in M prevails,
however, and all Me2Z compounds with the exception of Co2Z, which has planar
anisotropy, are uniaxial. Figure 2.9 (c) shows unit cell cross sections of Z-type
hexaferrites.
(v) X-type hexaferrite: X-type hexaferrites constructed as stack of hexagonal
R-block and spinel S-block along the hexagonal c-axis with a model as RSR*S*S*,
with the (*) indicating the rotation of corresponding block by 180 around the
c-axis. The structure of X-type compound is closely related to that of M and W type.
The X-type hexaferrite can be constructed by X = 2 M + S as seen from Figure 2.6.

- 22 -

(a)

(b)

(c)

Figure 2.8 The unit cell cross-sections of (a) M-type, (b) Y-type and (c) Z-type hexaferrites

(vi) U-type hexaferrite: U-type hexaferrite having general formula Ba4Me2Fe36O60

with Me a bivalent transition metal ions, is very difficult to prepare in single phase
condition owing to their complex crystalline structure. It can be constructed by
U = 2 M + Y as indicated in Table 2.1.

- 23 -

2.2 Properties of SrFe12O19

This M-type hexaferrite has a very large saturation magnetization, a large
uniaxial magnetic anisotropy, and a high curie temperature, which have been widely
used as permanent magnetic materials. Strontium hexaferrite powders can exhibit a
high coercivity due to the relatively high magneto-crystalline anisotropy field. Some
standard properties of SrFe12O19 are given in this section.

2.2.1 Structural properties

Molecular Formula

SrFe12O19

Molecular Weight

1061.75 g/mol

H-Bond Donor

H-Bond Acceptor

19

Exact Mass

1063.03

Mono Isotropic Mass

1063.03

Topological Polar Surface Area :

277

Heavy Atom Count

32

Formal Charge

Complexity

36.2

Covalently-Bonded Unit Count

2.2.2 Physical and Chemical properties

Colour

: dark brown

Morphology

: spherical

Bulk density

: 0.41-0.51 g/cm3

True density

: ~ 5.3 g/cm3

IUPAC Name

: oxo (oxoferriooxy) iron; oxostrontium

Space group

: P 63/mmc

Space group number

: 194,

Laue class

: 6/mmm

: 24

Centro-symmetric space group

: (x, y, z) = (-x, -y, - z)

Bravais translation

Primitive
- 24 -

2.2.3 Canonical SMILES (Simplified Molecular Input Line Entry

Specification) of SrFe12O19:
O = [Fe] O [Fe]] = OO = [Fe] O [Fe] = OO = [Fe] O [Fe] = O
O = [Fe] O [Fe] = OO = [Fe] O [Fe] = OO = [Sr] can be represented as
shown in Figure 2.10..

Figure 2.10 Canonical SMILES for SrFe12O19

2.2.4 Sublattices of SrFe12O19 hexaferrite with their point

symmetry and spin orientation
SrFe12O19 hexaferrite having five sublattice as described in crystal structure
of M-type ferrites. Table 2.3 represents thee type, point symmetry and their spin
directions with Blocks.
Table 2.3 Five iron sites, their spin direction, type, point symmetry, number of Fe ions per
formula, and block situation in SrFe12O19.

Sublattice

Type

12k

Octahedral

Point
symmetry
m

4f1

Tetrahedral

4f2

4
5

Sr.
No.
1

Spin
(5 B)
Up

3m

Down

Octahedral

3m

Down

2a

Octahedral

3m

Up

2b

Five Fold

6m2

Up

Ions/SrFe12O19

Block
SR

- 25 -

2.2.5 Atom coordinates (x, y, z) with Wyckoff letters

Table 2.4 Final results of the Rietveld refinement of SrFe12O19 in space group P 63/mmc;
Fractional Coordinates of Atoms in the Asymmetric Unit (x, y, z), g occupation factor.

Sr.
No.
1

Atom

Wyck. letter

Sr

2d

0.33

0.66

0.25

0.946

Fe1

2a

0.00

0.00

0.00

0.968

Fe2

2b

0.00

0.00

0.24

0.474

Fe3

4f1

0.33

0.66

0.97

0.972

Fe4

4f2

0.33

0.66

0.81

0.954

Fe5

12k

0.16

0.33

0.39

0.959

O1

4e

0.00

0.00

0.34

0.928

O2

4f

0.33

0.66

0.44

0.951

O3

6h

0.82

0.63

0.25

0.918

10

O4

12k

0.84

0.69

0.45

0.872

11

O5

12k

0.50

0.99

0.35

0.893

2.2.6 Bond length, Bond angles and lattice constants

Table 2.5 (a) Bond lengths, (b) bond angles, and (c) lattice constants from Rietveld
refinement for the standard SrFe12O19 sample

(a)

Sr.
No.

Type

Bond
length ()

Sr.
No.

Type

Bond
length ()

SrO

2.8601

10

Fe4O5

1.8916

SrFe2

3.3958

11

Fe5O1

2.0674

SrFe5

3.6478

12

Fe5O2

1.9511

Fe1O4

2.0058

13

Fe5O4

2.1241

Fe2O1

2.4583

14

Fe5O5

1.9336

Fe2O3

1.8904

15

Fe2Fe4

3.6661

Fe3O2

1.9171

16

Fe2Fe5

3.7123

Fe3O4

1.8792

17

Fe4Fe4

2.7672

Fe4O3

2.0302

18

Fe5Fe5

2.9860
- 26 -

(b)

(c)

Sr.
No.

Type

Bond angle
(deg)

Lattice
constants

Fe2 O1 Fe5

117.91

a = b = 5.8751

Fe3 O2 Fe5

126.22

c = 23.0395

Fe5 O1 Fe5

99.90

Fe5 O4 Fe5

89.34

V=688.71 3

2.3 Introduction of nano structured materials

Any property in a solid is associated with a particular length scale, and below
this length, the property will vary. When characteristic structural features are
intermediate in extent between isolated atoms and bulk materials, in the range of
about 10-9 to 10-7 m (1 to 100 nm), the objects often display physical attributes
substantially different from those displayed by either atoms or bulk materials. By
creating nanometer scale structures, it is possible to control fundamental properties of
materials like their melting temperature, magnetic properties, charge capacity, and
even their color, without changing the materials chemical composition. Properties of
matter at the nanoscale are not necessarily predictable from those observed at larger
scales. Important changes in behaviour are caused not only by continuous
modification of characteristics with diminishing size, but also by the emergence of
totally new phenomena such as quantum size confinement, wave-like transport, and
predominance of interfacial phenomena [10]. Utilizing the potential of nanoscale
structures leads to new, high-performance technologies that were not possible before;
which creates great opportunities for fundamental science in condensed matter
physics, solid state chemistry, materials science, electrical engineering, biology, and
other disciplines. In materials science, the nanometer length scale is the largest one
over which a crystal can be made essentially perfect.

2.3.1 Nano Particle Materials Research

Nano scale particle research has recently become a very important field in
materials science. Nano scale particles (10 to 100 nm) usually have physical
properties different from those of large particles (10-100 m) or the molecular/atomic
species. It has been found that nanoparticles exhibit a variety of previously
- 27 -

unavailable properties, depending on particle size, including magnetic, optical, and

other physical properties as well as surface reactivity. Recent experiments have shown
that consolidated nano-materials have improved mechanical properties, such as
increased hardness of metals and increased ductility and plasticity of ceramics. The
unique properties of nano scale particles and nano grain bulk materials can be
attributed to two basic phenomena. The first is that the number of atoms at the surface
and/or grain boundaries in these materials is comparable to that of the atoms located
in the crystal lattice, thus the chemical and physical properties are increasingly
dominated by the atoms at these locations. The second phenomenon is the quantumsize effect or quantum confinement effect. When particles approach the nanometer
size range, their electronic and photonic properties can be significantly modified as a
result of the absence of a few atoms in the lattice and the resulting relaxation of the
lattice structure.
During the last decade the field of Nanotechnology has emerged as a frontier
research area due to its enormous promise for novel applications to diverse fields of
human endeavour such as biomedical sciences (drug delivery, therapy, hyperthermia,
advanced imaging), defence (smart and light systems), aerospace (engineered surfaces
and composites), agriculture, energy (solar cells, fuel cells, batteries), environment
(gas, humidity, bio-sensors), consumer electronics and advanced device systems,
special paints and coatings etc. Intense research is now in progress worldwide to
realize this promise via controlled nano-synthesis, appropriate functionalization of
nano-materials, self assembly or template assembly of nanostructures, integrations of
nano-materials with other materials to generate functional nano-composites,
development and implementation of novel device concepts highlighting the special
quantum features of nano-materials and so on.
The development of uniform nanometer sized particles has been intensively
pursued because of their technological and fundamental scientific importance [11].
Nanoparticles is a term used for particles with diameters of 2-90 nm with variable
crystallinity. These nanoparticluate materials often exhibit very interesting electrical,
optical, magnetic and chemical properties, which cannot be achieved by their bulk
counterparts [12]. The synthesis of discrete magnetic nanoparticles with sizes ranging
from 10 to 100 nm, is of significant importance, because of their applications in multiterabit magnetic storage devices [13]. Such magnetic nanoparticles could also find
- 28 -

applications in ferrofluids, magnetic refrigeration systems, contrast enhancement in

magnetic resonance imaging, magnetic carriers for drug targeting and catalysis [14].
These nanoparticles can be dispersed in many organic solvents and can be retrieved as
powder forms by removing the solvent. Chemical methods have been widely used to
produce nano-structured materials due to their straightforward nature and their
potential to produce large quantities of the final product. There are several synthetic
procedures for synthesizing mono-dispersed nanoparticles. The particle sizes of
nanoparticles can be controlled by systematically adjusting the reaction parameters,
such as time, temperature and the concentrations of reagents and the nature of
stabilizing surfactants. In general, particle size increases with increasing reaction
time, because more monomeric species are generated, and with increasing reaction
temperature because the rate of reaction is increased.

2.4 Preparation methods of hexaferrites

Several techniques have been used to prepare strontium hexaferrite, including
the traditional solgel process [15], the solid-state method [16], the salt melting
method [17], ball milling [18], self-propagating high temperature synthesis [19],
chemical co-precipitation method [20], and the Microemulsion route [21]. Among the
various existing methods of chemical synthesis, micro emulsion route is an alternative
and promising technique for preparing the ferrites, leading to highly pure, chemically
homogeneous, nanometric scale particles.
Three different chemical routes are adopted in present work in order to
synthesize SrFe12O19 hexaferrite nanoparticles. They are chemical co-precipitation;
microemulsion and self propagating high temperature synthesis (SHS). The other
methods namely ceramic route, sol gel process etc. have the disadvantages like
particle inhomogenity, presence of impurity, larger grain size of the final product;
requirement of high temperature sintering, etc.

2.4.1 Co-precipitation method

The chemical co-precipitation method is usually used to synthesize magnetic
oxides due to its simplicity and good-control of grain size.

- 29 -

The metal salts are taken in the stoichiometric amount in the distilled water.
Vigorous stirring is required during the process. Alkaline solution of NaOH, NH4OH
or (NH4)2CO3 can be used as a precipitating agent. The pH of the solution should
reach >10. After the formation of dark brown coloured precipitates, the mixed
solution is kept ideally overnight for aging. Then the precursors are filtered out,
washed several times with distilled water and acetone with methanol. Then precursors
dried at 100 C for 24 hrs. Heat treatment is required to form the final phase. The
yield obtained with this method is 75%.
However, the average particle size obtained by this method ranges from
70-100 nm. Here, the approach is to prepare the homogeneous nanosized particles. So
surfactants of different kinds are used in order to make the smaller grain size
(~50-70 nm) with narrow size distribution.
It is observed that there exist some undesirable intermediate nonferromagnetic phases, which lead to poor magnetic properties and irregular shape of
the derived SrFe12O19 particles [22]. To remove such non-magnetic phases, here it is
tried to modify the sintering conditions from conventional heating in furnace to
microwave heating. To remove such non-magnetic phases, the sintering conditions are
changed from conventional heating to microwave heating.

2.4.2 Microemulsions/reverse micelles

Microemulsions are basically thermodynamically stable, optically transparent,
isotropic dispersions of aqueous and hydrocarbon liquids stabilized by an interfacial
film of surfactant molecules. They are monodispersed spherical droplets
(diameter < 100 nm) of water in oil (w/o) or oil in water (o/w), depending on the
nature of the surfactant. Reverse micelles are nanodroplets of water sustained in an
organic phase by a surfactant that can hold and dissolve inorganic salts. The inorganic
salts are then converted to an insoluble inorganic nanoparticle after chemical reaction
and removal of water. The chemical reactions that occur in the reverse micelles can be
precipitation or reduction reactions, depending on the products desired. In the
precipitation reaction, two reverse micelles containing the constituent ions of a
precipitate come in contact to each other upon mixing; this results in the formation of
the precipitate.

- 30 -

(b)
(a)

Figure 2.11 Schematic representation of Microemulsions:

Microemulsions (a) water in oil,
oil (b) oil in water

On a microscopic level, the mixtures are structured into waterwater rich and
oil-rich
rich domains separated by an amphiphilic film.
(a)

Stability of Microemulsions
Figure 2.12 shows the temperature dependence of emulsion.
emu
The best

stabilization condition for almost all emulsions is to keep the reaction temperature
50C [23].
Water

emulsion
oil
30 C

40 C

50 C

60 C

70 C 75 C

80 C

90 C 100 C

Figure 2.12 Temperature dependence of emulsion

(b)

Phase Behavior
Water in oil microemulsion technique is used for the controlled preparation of

very small and narrowly distributed nanoparticles.

anoparticles. Ternary mixtures, usually
consisting of water, a non-polar
non polar solvent (oil phase) and a surfactant are
thermodynamically stable, optically clear and isotropic one-phase
one phase solutions. In case of
w/o microemulsions nanometer sized water droplets are stabilized by a surfactant
monolayer and segregated by a continuous oil phase. These three component systems
exhibit a very complex phase behaviour often represented in a ternary phase diagram
(Gibbs triangle). In such a phase prism as shown in Figure 2.14 (a, b),
b) a multitude of

- 31 -

structures can be found: e.g., two- and three-phase regions, liquid crystalline phases as
well as microemulsion phases (one-phase regions) [24]. This method has gained
recent interest. Reverse micelles consist of aqueous nanometer sized droplets that are
separated from the bulk organic phase by a surfactant layer (Figure 2.13) [25]. This is
an isotropic and thermodynamically stable macroscopically single-phase system that
consists of three components: water, oil, and an amphiphillic molecule, the surfactant
[26]. In this approach, the micelles play the role of nanoreactors which provide
control over particle growth, shape, inter-particle spacing, and produce highly
uniform morphologies. Depending on the size of the micelle, particles typically range
from 2-10 nm in diameter and their magnetic behaviour can range from super
paramagnetic to ferromagnetic at larger size [27].

Figure 2.13 Schematic of a reverse micelle

The phase diagrams for microemulsions are quite complex as it requires at

least three components (and often four) namely, the oil, water (electrolyte solution)
and surfactant (and sometimes a co-surfactant). Temperature and pressure are
important factors in any situations.

(a)

(b)

Figure 2.14 (a) System of water/oil/surfactant (b) Phase diagram showing probable
emulsions with different concentration of water phase, oil phase, surfactant and co-surfactant.
- 32 -

(c)

Preparation of nano ferrites using a Microemulsion technique

Nanoparticle synthesis by use of the water-in-oil microemulsion technique

was first reported by Boutonnet et al. [28], who prepared 35 nm noble metal particles
in 1982. Water-in-oil microemulsions, also known as reverse micelles, have been used
to synthesize a variety of nanostructured materials, for example nanoparticles of silver
halides, superconductors, and magnetic oxide [29]. Water-in-oil microemulsion
provides a novel vehicle for synthesis of a micro-particulate oxalate precursor which
yields very high density sintered powder of ferric oxides. Static barrier by surfactant
monolayer restricts the growth of precipitated particles and hinders intergrain
coagulation.

Figure 2.15 Schematic representation of W/O microemulsion and the reaction mechanism

A schematic representation of water-in-oil microemulsion method is illustrated

in Figure 2.15. In the precipitation reaction, two reverse micelles containing the
constituent ions of a precipitate come in contact to each other upon mixing; this
- 33 -

results in the formation of the precipitate. The most frequently employed surfactants
are sodium bis (2-ethylhexyl) sulfosuccinate (NaAOT), cetyltrimethyl ammonium
bromide (CTAB), and didodecyl dimethyl ammonium bromide (DDAB). The
advantage of this method is that control of the physical and chemical properties of the
reverse micelle and microemulsion systems enables great control over particle size
with a narrow size distribution and shape.
Precipitation reactions with reverse micelles as templates are suitable for the
synthesis of nanoparticles of magnetic oxides. Synthesis of hexaferrite involves two
steps, preparation of nanoparticles of a precursor then calcination of the precursor to
preferred hexaferrite.
The mean crystallite sizes of hexaferrite particles can be produced by
microemulsion route is in the range 10 60 nm, depending on the reaction condition
i. e. water/oil ratio, salt concentration, temperature, and the period of time taken to
mix the two microemulsions [30].

2.4.3 Self propagating High temperature Synthesis (SHS)

technique
The Self propagating High temperature Synthesis (SHS) approach to prepare
nanosized ferrites is of great interest, because of the overall simplicity of the
technique. In general, these methods involve the preparation of a precursor using an
organic acid in aqueous solution which contains all necessary cations in the desired
product and combustible anions. After dehydration at mild temperatures the precursor
becomes a dry gel that is amorphous in nature. The dry gel directly yields the required
materials upon calcination in the presence of air or oxygen. Because the starting
materials are homogeneously mixed on an atomic scale in the solution during
precursor preparation, all the ions in the dry gel are homogeneously fixed in the
polymeric matrix with very short diffusion paths to each other. The formation of a
new phase occurs at a lower calcination temperature, in comparison with conventional
solid-state reaction. The SHS route promoted the formation of nanocrystalline M-type
hexaferrite at a lower temperature (950 C) than that employed by the conventional
methods (1200-1300 C). The advantages of hexaferrite preparation through SHS
route are: very simple, low cost method; sophisticated instruments are not needed;
- 34 -

energy saving method. It produces homogeneous, porous with high surface area
materials. The entire preparation process completes within few minutes (less than 5
min). By use of these methods, ultrafine powders of a large number of spinel, garnet,
and hexaferrites have been synthesized.

2.5 Surfactants
Surfactants are compounds that stabilize mixtures of oil and water by reducing
the surface tension at the interface between the oil and water molecules. Surfactants
are wetting agents that lower the surface tension of a liquid, allowing easier
spreading, and lower the interfacial tension between two liquids.
The colloidal systems composed of isolated particles with nanometer-sized
dimensions that are stabilized by surfactant molecules and dispersed in solvent media.
In the ideal case, these non-interacting systems derive their unique magnetic
properties mostly from the reduced size of the isolated nanoparticles, and
contributions from inter-particle interactions are negligible. The surfactant coating on
magnetic nanoparticles prevents clustering due to static repulsion. Dynamic
adsorption and desorption of surfactant molecules onto particle surfaces during
synthesis enables reactive species to be added onto the growing particles.

2.5.1 Classification of surfactants

Surfactants are molecules that possess a hydrophilic head group and a
hydrophobic tail group. They can be anionic, cationic, or nonionic in nature. All of
these factors contribute to the behaviour of surfactants in solution. Surfactants have a
tendency to self-assemble into structures that are dependent upon their character and
environment. These structures can be spheres, cylinders, ellipsoids, bilayers, vesicles,
hexagonal liquid crystals, lamellar sheets, wormlike entanglements, or intercontigous
networks, depending on the hydrophobic and hydrophilic interactions at the
hydrophilic-water interface [31]. A surfactant molecule lowers the interfacial tension
between water and oil resulting in the formation of a transparent or translucent
solution [32].

- 35 -

(a)

(b)

Figure 2.16 (a) ionic surfactant and (b) non-ionic surfactant

Figure 2.16 shows surfactants on the surface of particles: (a) Ionic surfactants
produce charged surfaces and (b) Nonionic surfactants produce protective coatings.
The concentration at which surfactants begin to form micelles is known as the
critical micelle concentration or CMC. When micelles form in water, their tails form a
core that can encapsulate an oil droplet, and their (ionic/polar) heads form an outer
shell that maintains favourable contact with water. When surfactants assemble in oil,
the aggregate is referred to as a reverse micelle. In a reverse micelle, the heads are in
the core and the tails maintain favourable contact with oil.
Addition of cationic surfactant with hydrophilic head and hydrophobic tail into
the solution results in formation of reverse micelles. Placing the aqueous ions inside
these micelles can be effective in controlling the nucleation and growth of the
particles. Due to the existence of surfactant, the surface tension of solution is also
reduced, which reduces the energy of the formation of the new phase [33].
Three different surfactants (cationic, anionic and non-ionic) are used in
present work are described below with their specifications.
CTAB
Type: Cationic
Full Name: Hexadecyl
trimethyl ammonium
bromide
Molecular Formula: CH3(CH2)15N(Br)(CH3)3
Molecular Weight: 364.5 g/mol

- 36 -

SDS
Type: Anionic
Full Name: Sodium
Dodecyl Sulfate
Molecular Formula:
C12H25NaO4S
Molecular Weight: 288.38 g/mol

TRITON X-100
Type: Non-ionic
Full Name: Octyl phenol poly
(ethylene glycolether)x
Molecular Formula: C34H62O11
Molecular Weight: 647 g/mol

TWEEN-80
Type: Non-ionic
Full Name: Polyethylene (20)
sorbitan monooleate
Molecular Formula: C64H124O26
Molecular Weight: 1310
13 g/mol

2.6 Swift Heavy Ion irradiation

Energetic ions play a vital role in materials science as they can produce
systems away from the thermodynamic equilibrium. The ions in different energy
regimes, ranging from a few hundreds of eV to a few hundreds of MeV have different
roles in materials. Broadly, these energetic ions are useful in different ways:

- 37 -

(1) Synthesis of materials

(2) Modification of materials
(3) Characterization of materials
Defect engineering in materials is of importance. The two parameters of ion
beam, which crucial role in defect engineering, are the ion mass and its energy, which
decide the magnitudes of the electronic as well as nuclear energy losses.
Interaction of radiant energy with matter, especially Swift Heavy Ion (SHI)
irradiation, is extremely important problem from the viewpoint of theory and practice.
Elementary charged particles and electromagnetic radiation with high energy interact
with an electronic shell or the atomic nuclei of the substances passing through them.
These interactions results in an elastic and inelastic scattering of the particles attended
by excitation and ionization of the atoms, as well as the initiation of nuclear reactions
and also disturbance in the structure of matter, the so-called radiation damage. Two
models of microscopic energy transfer mechanism; thermal spike [34] and the ionic
spike [35] have been used to establish the relevant parameters governing the basic
energy transfer process.
The term SHI here refers to the energetic ions having energy in the range of a
few tens of millions electron volts (MeV) to giga electron volts (GeV). During last
two decades considerable research work has been carried out on the effect of SHI on
the structural and physical properties of magnetic insulators like ferrites. The
crystallographic and magnetic changes in bulk samples induced by irradiation are
known for various kinds of radiation, such as fast neutron, low energy ions, high
energy ions for different kinds of ferrites structure, such as spinel, garnets and
hexaferrites.
It has been shown through the study of SHI irradiation of magnetic insulators
that irradiation of solids with the energetic particle beams leads to the creation of a
wide variety of defect states (point defects, clusters of defects, phase change like
amorphization of crystal) leading to the modifications on their physical properties. It
has been demonstrated that in the ion energy regime for which the electronic energy
loss (Se) dominates over the nuclear energy loss (Sn), above specific energy threshold,
the damage created by the high electronic excitation induced by SHI in insulators
results in formation of the defected regions.
- 38 -

In ion irradiation, energetic ions are directed on a target material to initiate

changes in its physical, structural and transport properties. This method of materials
modification is non-equilibrium in nature, hence interesting, and a wide class of
materials like metals, semiconductors, ceramics, and ferrites has been found sensitive
to the technique. Study of the process of irradiation has two broad aspects:
(1) Study of nature of interaction and qualitative nature of damage created by the
process
(2) Quantify the damage created under controlled conditions.
These studies would help in diverse research goals: to induce grain refinement,
provide nucleation sites, form precipitates, create amorphous phase and variety of
other stochiometric or structural alterations of materials. The above-mentioned studies
are bulk changes of materials whereas one could also think of surface modification,
which is an important part of materials research. Surface modification can be
achieved using techniques such as ion implantation, ion beam mixing, low-energy ion
deposition and ion beam annealing.
In the last decade, focus has been shifted to the fundamentals of ion-solid
interaction. This shift is due to increasing need to utilize beams to modify materials
for specific applications. The interaction of the ion beam with solid is a nonequilibrium process. When an energetic ion penetrates a target, it loses its energy via
two nearly independent processes:
(1) Inelastic collisions of the highly charged energetic ions with atomic electrons of
the matter [electronic energy loss (dE/dx)e] and
(2) Elastic scattering from nuclei of atom of the matter [nuclear energy loss
(dE/dx)n].
In the inelastic collision (cross-section 10-16 cm2) energy is transferred from
the projectile to atom of the matter through excitation and ionization of their
surrounding electrons. The amount of electronic energy loss in each collision varies
from eV/ to a few keV/. For a swift heavy ion (SHI) moving at a velocity
comparable to the Bohr velocity of electron, this is dominant mechanism for transfer
of energy to the material causing the modification of its properties. The nature of

- 39 -

modification depends upon the electrical, thermal and structural properties of the
target material, the mass of the projectile ion and irradiation parameters [36].
Irradiation by various kinds of particles like electrons, -photons, fast
neutrons, protons, low energy ion and high energy ions on magnetic oxides causes
micro-structural defects and disorder, which affect magnetic, electric and dielectric
properties. The work available in the literature deals with irradiation effects on
various properties of polycrystalline, single crystal, thin films and nanoparticles of
magnetic oxides like ferrites. In materials like garnet, spinel and hexaferrites, the
properties are very sensitive to the irradiation-induced disorder, which results in a
decrease of the saturation magnetization [37]. In recent years, attention has been
devoted towards the swift heavy ion irradiation induced modifications in the ferrite
nanoparticles.
The passage of SHI in materials mainly produces electronic excitation of the
atoms in the materials. SHI causes exotic effects in different classes of materials
which otherwise cannot be generated by any other means. Quantitatively, it is capable
of depositing electronic excitation energy of about 1 to 10 keV/ in the materials.
Such a large electronic excitation brings out various changes in materials. Swift heavy
ions (SHI) lose energy in materials mainly through inelastic collisions with the atomic
electrons. Along the trajectory, a trail of defects (point defects, defect clusters,
structural phase transformation) known as latent track may be formed depending on
the type of ion and its energy as well as the physical property of the materials. This
damage is always created in the close vicinity of the trajectory of projectile. With the
availability of high energy heavy ions from modern accelerators, swift heavy ion
beams are proving to be of immense use in various fields, particularly for
modification of materials through dense electronic excitation following the slowing
down of swift heavy ions in material. The passage of SHI induces very rapidly
developing processes which are difficult to observe during or immediately after their
occurrence. The information about these processes is stored in the resulting damage,
such as size, shape and structure of defects. The degree of disorder can range from
point defects to a continuous amorphized zone along the ion path, commonly called
latent track.

- 40 -

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