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Chapter - 2: Crystal Structure, Preparation Techniques and Swift Heavy Ions Irradiation
Chapter - 2: Crystal Structure, Preparation Techniques and Swift Heavy Ions Irradiation
Chapter - 2: Crystal Structure, Preparation Techniques and Swift Heavy Ions Irradiation
Crystal Structure,
Preparation techniques
and
Swift heavy ions irradiation
Sr.
No.
Types
Crystal
structure
General
formula
Replacements
Spinel
Cubic
AIIFe2O4
Garnet
Cubic
LnIII3Fe5O12
Ortho ferrite
Perovskite
LnIIIFeO3
Magnetoplumbite
Hexagonal
AIIFe12O19
- 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)
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.
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.
(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].
- 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
- 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*
TSTST
RSSR*S*S*
RSTSR*S*T*S*
RSR*S*S*
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.
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 -
- 22 -
(a)
(b)
(c)
Figure 2.8 The unit cell cross-sections of (a) M-type, (b) Y-type and (c) Z-type hexaferrites
- 23 -
SrFe12O19
Molecular Weight
1061.75 g/mol
H-Bond Donor
H-Bond Acceptor
19
Exact Mass
1063.03
1063.03
277
32
Formal Charge
Complexity
36.2
: dark brown
Morphology
: spherical
Bulk density
: 0.41-0.51 g/cm3
True density
: ~ 5.3 g/cm3
IUPAC Name
Space group
: P 63/mmc
: 194,
Laue class
: 6/mmm
: 24
Bravais translation
Primitive
- 24 -
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 -
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
(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
- 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.
- 30 -
(b)
(a)
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
(b)
Phase Behavior
Water in oil microemulsion technique is used for the controlled preparation 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].
(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)
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
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].
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.
- 35 -
(a)
(b)
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
- 37 -
- 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 -
References
[1]
A. Goldman, Modern Ferrite Technology, Van Nostrand Reinhold, New York, 1990.
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
- 41 -
- 42 -