ABSTRACT

In the present work I report the preparation of Magnetic Nanoparticles by CoPrecipitation technique. The hydroxyl ion concentration was varied by taking different
molar concentrations of alkali solvents in the precursor solution. The synthesized
materials were studied by using XRD, FTIR spectrometer

and Vibrating Sample

Magnetometer (VSM) techniques. The VSM studies of these nanoparticles shows

superparamagnetic behavior which confirms their nanometer size. FTIR studies

confirm the formation of Fe-O and O-H bond stretching Peaks.

31Page

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ip
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'I

tONTENTS
L An Overview of Nanotechnology
1.1 Introduction
1.2 Nanomaterials
1.2.1 General
~2.2 Organic
1.2.3 Inorganic
1.2.4 Nanoparticles

1.3 Magnetic Nanoparticles

1.3.1 Metals

L3.2 MagneticNanoparticles inside Usand EverywhereAround Us

1.3.3 Oxidation of Metallic Nanoparticles
1.3.4 MagneticAlloys
1.3.5 Magnetic Oxides

2. Experimental
2.1 Introduction
2.2 Synthesis of Iron-Oxide Nanoparticles
2.2.1 Co-Precipitation
2.2.2 Thermal Decomposition
2.2.3 Microemulsion
2.2.4 Hydrothermal Synthesis
2.2.5 Sonochemical Synthesis

23 Characterization Techniques
2.3.1 Fourier Transform Infrared Spectroscopy (FTIR)
2.3.2 Powder X-Ray Diffraction (XRD)
2.3.3Vibrating Sample Magnetometer (VSM)

2.4 Preparation Fe304 Nanoparticles

2.4.1 Introduction
2.4.2 Experimental

5
5
6
6
7
7
7
9
9
11
12
12
13
HI

17
17
17
18
19
19
20
20
22
22
25
32
35
35
36

11i

I~
I~

I;

"
:~
IiI
\11

I:
Jl,

3. Results and Discussion

3.1 FTlR Studies
3.2 Powder X-Ray DiffractionStudies
3.3 Vibrating Sample Magnetometer Studies

37
37
39
43

4. Conclusions

44

s. References

45
41Page

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1:-

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...

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..

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1. An Overview of Nanotechnology

1.1 INTRODUCTION

.
..
..

,
r

In 1959, the
nanotechnology

great physicists, Professor Richard Feynman give the first talk on the

in his lecture

"There's

Plenty of room at bottom"

he never used the word of

...

nanotechnology, Feynman only talked about a number of interesting methods to generate the

matter of atomic scale and he is interested to see things much smaller than is possible with

-scanning electron microscope" and "scanning tunneling microscope" that are today's modified

..
..

examples but the Feynman did not explain the full concept of nanotechnology he only give the

origin of nanotechnology.

..
..

,
,
,

..

,.

In 1974, the term nanotechnology was used by Tokyo Science University Professor Norio
Ta.niguchito manufacturing the materials at nanometer level such as structures having at least one

dimension in range of 1-100 nm or 1 nm =10

-9

m are defined as nanomaterials. Basically

nanotechnology is employed to describe the creation and exploitation of materials with structural
features in between those of atoms and bulk materials.
The properties of materials which are in nanometer dimensions are significantly different

from those of atoms as well as those of bulk materials. These materials are becoming the important

for the point of both for understanding the fundamentals in science to explain exciting new

properties together with development of new product of multiple functional~ties. . It will offer
better built, longer lasting, cleaner, safer, and smarter products for the home, for communications,
for mecflCine,for transportation, for agriculture, and for industry in general. A key understanding of
nanotec:hnology is that it offers not just better products, but a vastly improved manufacturing
and it also covers the fields from biology to material.science, physics to chemistry, and can
indude development in a variety of specialties.

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-----.

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SIPage

1.2 NANOMATERIALS
1.2.1 General
During the last decade, due to the emergence of new generation of high-technology material,
the number of research group involved in nanomaterials has increased exponentially. The need of
new nanomaterials with potential properties has always been the driving force for the progress in
several fields in science and technology. Nanomaterials has played great role in several domains
such as chemistry, electronics, high-density magnetic recording media, sensor biotechnology, and it
is also responsible for the many great changes and new research opportunities in physics, chemistry,
material science, biology etc. During the past few years, many new nanomaterials have been
synthesized for several technological oriented applications.
Basically nanomaterials are divided in two categories: Fullerenes and nanoparticles (fullerenes
are carbon nanotubes, fullerene, and allotropes of carbon etc, and,nanoparticles are nanostructure,
colloidal gold, silver nanoparticles, iron nanoparticles, plotline nanoparticles).

There are thousands of nanomaterials in various structure forms e.g. Quantum dots, wire tubes,
fibers etc. have been synthesized and reported to show exciting surface, optical, electrical, magnetic
and mechanicals properties.
However, in addition to understanding the origin of the unusual properties in nanoparticles,
the three other associated areas witch need serious attentions are:
1) Identification and development of suitable preparation method especially those which are

scalable to prove large quantitiesof nanomaterials.

2) Development of processing method for manufacturing these materials into useful sizes and
shapes without lousing other desirable nanometer size features.
3) Identification of characterization methods since the nanometer size range just fall short or
at the res,olution limit of conventional tools.

Nanomaterials which could be polycrystalline or amorphous in nature may belong to:

61Page

1.2.2 Organic
Organi'; nanostructures are formed by smaller organic molecules via chemical or non-chemical
bonds to shc'w a variety of functional materials such as:

I'vlicro-or macroscopic structures made up of stacked plates with surface properties that
directly reflected the chemical exterior of flat nanostructures.

Cables or microfibers formed by aligned nanotubes that could select and direct molecules
or ions in space.

Microscopic objects or lithographically

fabricated

domains made up of super lattices from

nanostructures such as calixaranes, rotaxanes, etc.

1.2.3 Inorganic
Common examples of inorganic nanoparticles include metal and alloy, semiconducting oxide;
magnetic oxides (ferrites, ferrofluids) etc. Properties in inorganic nanomaterials are correlated to:

Comparability in size of nanoparticles with correlation scale of some physical phenomenon.

Characteristic length of some transport process.
Peculiar structure and abnormal phase states.
Comparability of number of atom on the surface and total number of atoms in the particles.

1.2.4 Nanoparticles
Nanoparticles and metal clusters represent an important state of condensed matter. Such
systems display many peculiarities and physical and chemical properties that were never observed
earlier. Nanoparticles may be considered as intermediate

formations, which are limited by

individual atoms on the one hand, and the solid phase on the other. Such particles exhibit the size

dependence and a wide spectrum of properties. Thus, nanoparticles can be defined as entities
.

measuring from 1 to 100 nm and built of atoms of one or several elements. Presumably, they
represent closely packed particles of random shapes with a sort of structural organization.
Nanoparticles are larger than individual atoms and molecules but are smaller than bulk solid. Hence
they obey neither absolute quantum chemistry nor laws of classical physics and have properties that
differ markedly from those expected. There are two major phenomenon's that are responsible for
'N,'c,',_~~~~,~.

71Page

these differences. First is the high dispersity of Nano crystalline systems. As the size of a crystal is
reduced, the number of atoms at the surface of the crystal compared to the number of atoms in the
aystal

itself, increases. Th(' second

phenomenon

occurs noticeably only in metals and

semiconductors. It is called'size quantization and arises because the size of a nanoparticle is

comparable to the de Brogli(:wavelength of its charge carriers (i.e. electrons and holes). Due to the
spatial confinement of the charge carriers, the edge of the valance and conduction bands split into
discrete, quantized, electronic levels. These electronic levels are similar to those in atoms and
molecules.
When dealing with nanoparticles, magnetic properties (and other physical ones) are size
dependent to a large extent. Therefore, particles whose size are comparable with (or less than) the
size of magnetic domains in the corresponding bulk materials are the most interesting form a
magnetism science viewpoint. A nanoparticle is a quasi-zero-dimensional (OD)Nano object in which
all characteristic linear dimensions are of the same order of magnitude (not more than lOOnm).
Nanoparticles can basically differ in their magnetic properties from larger particles properties.
Nanoparticles with a clearly arrangement

of atoms (or ions) are called Nano crystallites.

Nanoparticles with a clear-cut discrete electronic energy are often referred to as "quantum dots" or
-artificial atoms"; most often they have compositions of typical semiconductor materials, but not
always. Many magnetic nanoparticles have the same set of electronic levels.
Nanoparticles are of great scientific interest because they represent

a bridge between bulk

materials, molecules and structure at an atomic level. The term "clusters" which is currently used to
designate small nanoparticles with size less than Inm are Nanoparticles, which always have the
distribution

in sizes; molecular

magnetic clusters

are the fully identical small magnetic

nanoparticles. Their magnetism is usually described in term of exchange-modified paramagnetism.

Nano rods and nanowires are quasi-one-dimensional

(lD) Nano objects. In these systems, one

dimension exceeds by an order of magnitude the other two dimensions, which are in the Nano
range. The group of two-dimensional objects (2D) includes planer structure-Nano disks, thin-filmmagnetic structures, magnetic nanoparticles layers etc., in which two dimensions are an order of
magnitude grea-ter than the third one, which is in the nanometer range. For magnetic nanoparticles,
this value coincides (or less) with a size of magnetic domain in most bulk magnetic materials.

81Page
1~
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1.3 Magnetic Nanoparticles (Fe304)

There are much general methods have been developed for t he synthesis of nanoparticles and
most of them can be used for the preparation of magnetic particles, but an essential feature of their
synthesis is that the preparation of particles of a specified size and shape; at least the dispersity
should be small (5%-10%) and controllable.

The blocking temperature

(and other

magnetic

characteristics) also depends on the practice size. The possibility of shape controlled and anisotropic
magnetic structures synthesis are especially important and it is also important that the distance
between the particles in the matrix should be controllable.
The method of nanoparticles preparation cannot be detached from stabilization methods. For 110nm particles with a high surface energy, it is difficult to select a really inter median, because the
surface of each nanoparticles

bears the product of its chemical modification,

which affect

appreciably the nanomaterials properties. This is especially important for magnetic nanoparticles in
which the modified surface layer may posses' magnetic characteristics markedly differing from
those the particle core. The general methods for nanoparticles synthesis are related directly to the
stabilization and the special methods exist where the nanoparticles formation is accompanied by
stabirlzation.
There are a wide range of the magnetic nanoparticles, nanoparticles of magnetic metals, simple
and complex magnetic oxides, and alloys.

1.3.1 Metals
The metallic nanoparticles have larger magnetization compared to metal oxides, which is
interesting for many applications. But metallic magnetic nanoparticles are not air stable, and are

easily oxidized, resulting in the change or loss (fully or partially) of their magnetization. Here some

metals are given which shows the magnetic properties.

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91Page

Iron metal (Fe)

Iron is a ferrOrilagnetic material with high magnetic moment density (about 220emu/g)
and is magnetically ~oft. Iron nanoparticles

in the size range below than 20nm are the

superparamagnetic.
The common chemical methods used for the preparations include thermal decomposition
of Fe(CO)s(the particles so prepared are extremely reactive), reductive decomposition of some iron
(II)salts, or reduction of iron (III)acetylacetonate;

there is a chemical reduction with TOPOcapping.

The sonochemical method of reducing metal salts by NaBH4 had been widely used to
synthesize iron-containing nanoparticles in organic solvents. Well-dispersed colloidal iron is required
for applications in biological system such as MRIcontrast enhancement and biomaterials separation.
Nevertheless, the synthesis has yet a difficulty in producing stable Fe nanoparticles dispersion,
especially aqueous dispersions for potential biomedical applications.
The X-ray diffraction pattern of the powder form did not display any sharp maxima,
indicating the absence of crystalline phase. It was assumed that amorphization with due to the high
content of carbon in the nanoparticles studied. To prevent the iron oxide nanoparticles from
agglomerating, dispersing agent were added during synthesis, as a rule polyvinylpyrolidone (PVP).
The size dispersion of the nanoparticles produced using physical methods is broader than that in
nanoparticles synthesized by chemical methods like reverse micelle, co precipitation, etc.
Cobalt metal (Co)

Co nanoparticles depending upon the synthetic route are observed in at least three crystallographic
phase: typical for bulk Co HCP, cubic, or &-COcubic, or multiply twinned FCC-based icosahedral.
Conaltions of synthesis reactions are influence on the final product structure; in rare cases of the
determined face nanoparticles can be obtained. Often a size and phase selection was required to be
obtaining Co nanocrystals with a specific size and even shape.
A popular approach is to synthesize colloidal particles by inversed micelle synthesis; the inverse
micelles are defined as a microreacter. In order to obtain stable cobalt nanoparticles with a narrow
C'-~'--~~~_V~__~~"~~~~'_"'__~_~A~~

10 I P age

size distribution, Co(AOTh reverse micelles are used; their reduction is obtained by using NaBH4as

a reducingagent. Such particles are stabilized by surfactants and are often monodispersed in size, .
but are also unstable unless kept in a solution. Nevertheless, the chemical surface treatment by
lauric acid highly improves the stability and cobalt nanoparticles

could be stored without

aggregation or oxidation for at least one week. In many instance it is possible to obtain Co
nanoparticles coated by other ligands, which can be either dispersed in a solvent or deposited on a
substrate; in the latter case, self- organized monolayers having a hexagonal structure can be obtain.
In some instances of reduction with NaBH4it is possible to obtain Co-B nanoparticles. The size,
composition, and structure of this kind of nanoparticles strongly depend on the concentration of the
solution, pH, and the mixing procedure. It is well-known that the presences of oxides in magnetic
materials, which form spontaneously when the metallic surface is in contact with oxygen, drastically
change the metallic behavior of the particles. An enhanced magneto-resistance,

arising from the

uniform Co core size and CoO shell thickness, has been reported. This effect is caused by the strong
exchange coupling between the ferromagnetic Co core and the antiferromagnetic CoO layer.
Nickel metal (Ni)

The nano-sized ferromagnetic Ni is also being widely studied in an interest for fundamental
sciences and an interest for application such as magnetic storage, Ferro fluids, medical diagnosis,

":11

multilayer capacitors, and especially catalysis. Because these properties and application can be
II

tuned by manipulating the size and structure of the particle, the development of flexible and precise
synthetic routes has been an active area of research. At present, Ni nanoparticles are generally
prepared by Microemulsion techniques, using cetyltrimethyammonium

bromide or by reduction of

Ni ions in the presence of alkyl amines or trioctyphosphine oxide. The surface of Ni-nanoparticles

':1

was readily oxidation to NiO. On the basis of this discovery, they envisioned that the synthesis of
larger-sized Ni nanoparticles and their subsequent oxidation would provide a NiO shell high affinity
for bio molecular.

U.2

Magnetic Nanoparticles

inside Us and Everywhere Around Us

The magnetic nanoparticles are found around and inside us such as interstellar space, lunar
samples, and meteorites have inclusive magnetic nanoparticles. The geomagnetic navigational aids
.~~~-

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II

in all migratory bird, fishes and other animals contain magnetic nanoparticles. The most common
iron storage protei~ ferritin ([FeOOH] in containing magnetic nanoparticles) is present in almost
every cell of plan.s and animals including humans. The human brain contains 108 magnetic
nanoparticles of rrlagnetic-maghemite per gram of tissue.

1.3.3 Oxidation of Metallic Nanoparticles

Magnetic properties of metallic nanoparticles are dependent on the degree of oxidation is
necessary for the forecasting of magnetic characteristics of obtained samples. However, as the
experiments have shown, it was often difficult. It should be noted that the oxidation of magnetic
metal nanoparticles during their synthesis cannot be avoided completely. If the deposition of
oxygen present in the gas phase in trace amounts on the nanoparticles surface cannot be avoided
even under these "exceptional" conditions, it is evident that under "usual" conditions, the
nanoparticles of magnetic metal will always contain some amount of oxides or sub-oxide on the
surface. At same time the oxidation of amorphous Fel-xCxnanoparticles obtained by thermal
decomposition of Fe(CO)sin the decline in the presence of the oleic acid for several weeks in air has
shown that the particles having a spherical shape and a very narrow size distribution consist of a
and V-F~03.

1.3.4 Magnetic Alloys

Fe-Co Alloys

It is well known that Co and Fe form a body-centered-cubic

solid solution (COxFelOO-x)

over an

extensive range. The ordered Co-Fe alloys are excellent soft magnetic materials with negligible
magneto crystalline anisotropy. The saturation magnetization of Fe-Co alloys reaches a maximum at
Co content of 35 at. %; other magnetic characteristics of these metals also increase when they are
mixed. Therefore, Fe-Co nanoparticles attract considerable attention.

'_~~"~'~___'__"O_~~~~A_

12 I P age

Fe-Ni Alloys

The bulk samples of the iron-nickel alloys are either nonmagnetic or magnetically soft ferromagnets.
The Fe-Ni nanoparticles have a much lower saturation magnetization than the corresponding bulk
samples over the whole concentration range. An alloy containing37% of Ni has a low Curie point and
an FCC structure.

It consists of nanoparticles

(12-80nm) superparamagnetic

over a broad

temperature range.
Fe-Pt Alloys

Nanoparticles of this composition have received much attention in recent years due to the
prospects for a substantial increase in the information recording density for materials based on
them. The face-centered tetragonal Fe-Pt alloy possesses very high uniaxial magneto crystalline
anisotropy of ca.6x106J/m3, which is 10 times as high as that of the currently utilized Co-Cr-based
alloys and thus exhibit large coactivity at room temperature, even when their size is very small.
These unique properties make them possible candidates for the next generation of magnetic
storage and high-performance permanent magnets. For these syntheses the most commonly used
in the thermal decomposition of organometallic precursors or reduction of metal salts in the
presence of long-chain acid or amine and phosphine or phosphine oxide ligands.

1.3.5 Magnetic Oxides

Iron Oxides

Iron oxides have received increasing attention due to their extensive applications, such as
magnetic recording media, catalysts, pigments, gas sensors, optical devices, and electromagnetic
devices. They exist in a rich variety of structures and hydration states; therefore until recently,
knowledge of the structural details, thermodynamics and reactivity of iron oxides has been lacking.
Furthermore, physical (magnetic) and chemical properties commonly change with particle size and
degree of hydration. By definition, superparamagnetic

iron oxide particles (SPIO), displaying

hydrodynamic diameters larger than 30 nm, and ultra-small superparamagnetic

iron oxide particle

(USPIO),with hydrodynamic diameters small than 30 nm. USPIOparticles are now efficient contrast
-'~~.~-

13lpage

agents used to enhance relaxation differences between healthy and pathological tissues due to their
high saturation magnetization, high magnetic susceptibility, and low toxicity. The bio-distribution
and resulting .:ontrast of these particles are highly dependent on their synthetic route, shape and
size. High quality iron oxide nanomaterials have been generating using high temperature solution
phase methods similar to those used in semiconductor quantum dots. Other synthesis method such
as polyol-mediated, sol-gen and sonochemical were also proposed. The magnetic nanocrystals were
easily purified using stranded methods also developed for quantum dots.
For verity of magnetic nanomaterials

properties the different morphologies including

spheres, rods, tubes, wires belts, cubes, star like, flowerlike and other hierarchical nanoparticles
architectures were fabricate by various approaches.
Fez~
Among several crystalline modification anhydrous ferric oxides there are two magnetic
phases, namely, rhombohedral hematite (a-Fe203) and the less common V-Fe203phases. In the astructure, all Fe3+ions have an octahedral coordination, whereas in E-Fe203having the structure of a
cation-deficit AB204spinal, the metal atoms A and B occur in tetrahedral

and octahedral

coordination, environment, respectively. The oxide a-Fe203 is antiferromagnetic at temperatures

below 9S0K, while above the Morin point (260K) it exhibits so-called weak ferromagnetism.
Hematite, the thermodynamically stable crystallographic phase of iron oxide with a band gap of
2.2Ev, is a very attractive material because of its wide application, except magnetic recording
materials, also in catalysis, as a gas sensors, pigments, and paints. Its nontoxicity is attractive
features for these applications.
The a-Fe203 and FeOOH (goethite) nanoparticles are obtained by controlled hydrolysis of
fe3+ salts. In order to avoid the formation of other phases, a solution of ammonia is added to a
boiling aqueous solution of Fe(N03h with intensive stirring. After boiling for 2.5 h and treating with
ammonium oxalate (to remove the impurities of other oxide), precipitate forms a red powder
containing a-Fe203 nanoparticles {20 nm. These nanoparticles are also formed on treatment of
solutions of iron salts (Fe2+:Fe3+=1:2)with an aqueous solution of ammonium hydroxide in air.

14 I P age

A bulk y-Fe203 sample is a ferrimagnet below 620C. The y-Fe203 nanoparticles (4-16nm)

with a relatively narrow size distribution

have been obtained

by mild oxidation (Me3NO) of

performed metallic nanoparticles. The same result can be attained by direct introduction of (CO)s in
to a heated solution of Me3NO. The oxidation with air is also used to prepare y-Fe203 nanoparticles.
For this purpose, the Fe304 nanoparticles (9nm) are boiled in water at pH 12-13.
The most popular route to y-Fe203 nanoparticles is thermal decomposition of Fe3+salts in
various media .For example, good results have been obtained by using iron complexes with
cupferron. An iron power was milled in a planetary mill with water this is a convenient one stage
synthesis of magnetite nanoparticles (15nm).
A,dditionally, nonspherical Fe203 nanoparticles, such as nanorods, nanowire, nanobelts,
have also been synthesized and used for investigating their peculiar magnetic properties.
F1!30..(Magnetite)

Among all iron oxides, magnetite Fe304 possess the most interesting properties because of
the presence of iron cation in two balance states, Fe2-and Fe3-in the inverse spinel structure. The
cubic spinel Fe203 is ferromagnetic at temperatures below 858K. The route to these particles and
most often involves treatment of a solution of a mixture of iron salts (Fe2+and Fe3+)with a base
under an inert atmosphere. For example, the addition of aqueous treatment of a solution of FeCh
and Fe03 (1:2) yields nanoparticles which are transferred into a hexane solution by treatment with
oleic acid. The repeated selective precipitation gives Fe304 nanoparticles with a rather nano-sized
distribution. The synthesis can be performed starting only form FeCb, but in this case, a specified
amount of an oxidant (NaN02) should be added to the aqueous solution apart from alkali. This
method allows one to very both the particle size (6.5-38nm) and the particle shape.
In some cases, decomposition of compounds containing Fe3+ions under oxygen-deficient
condition is accomplished by partial reduction of Fe2+to Fe3+.Thus thermolysis of Fe(acach in
diphenyl ether in the presence of small amount of hexadecane gives very fine Fe304 nanoparticles
(about 1nm), which. can be enlarged by adding excess Fe(acach in to the reaction mixture. Fe304
nanoparticle can be also prepared in uniform sizes of about 9nm by autoclave heating the mixture,
consisting of FeCI3, ethylene glycol, sodium acetate and polyethylene

glycol. The reaction of

15 I P age

Fe(acach with hydrazine is carried out in the presence of surfactant. This procedure result in
superpa~amagnetic magnetite nanoparticles with controlled sized, 8 and 11 nm.
.

irhe dry methods are used along sizewith the solution ones.Thus,Fe304nanoparticleswith

an average size of 3.snm have been prepared by thermal decomposition of Fe2(C204h.5H20 at

T>400C. Furthermore, the controlled reduction of ultra-reduction a- Fe203in a hydrogen stream at
723 K is a more reliable method of synthesis of Fe304nanoparticles.

Ferrites
Microcrystalline ferrites from the basis of materials currently used for magnetic information
recorded and storage. To increase the recorded information density, it seems reasonable to obtain
Nano crystalline

ferrites

and.. to

prepare

magnetic

carriers

based on them.

Grinding

of

microcrystalline ferrite powers to reach the Nano sized of grains is inefficient, as this gives particles
with a board size distribution, the content of the fraction with the optimal particle size (30-50 nm)
being relative low.
The key method for the preparation of powders of magnetic hexagonal ferrites with a grain
size of more than 11..lmincludes heating of a mixture of the starting compounds at temperature
above 10000C (so-called ceramic method). Nano crystalline ferrites are often prepared by the co
precipitation

method.

Co precipitation

Ba(02C7H1Shunder ultrasonic treatment

upon decomposition

of a mixture

of Fe(CO)s and

has been successfully used for the synthesis of barium

ferrite nanoparticles ("'50 nm).

Method for the preparation of the ferrite nanoparticles of different compositions in solution
at moderate temperat~res

has been developed. First, worth mentioning is the sol-gel method

resulting in high dispersed powders with

required

purity and homogeneity.

Low annealing

temperatures allow one to control crystallization and to obtain the single-domain magnetic ferrite
nanoparticles with narrow size distributions

(smaller than 100 nm) and, Zn-, Ti-, and Ir-doped

strontium ferrite particle with a similar size.

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16 1 P age

2. Experimental
2.1 Introduction
In the last decades, surface functionalized magnetic iron oxide nanoparticles (Nanoparticles) are
a kind of novel functional materials, which have widely used in the biotechnology and catalysis. The
recent development and various strategies in preparation, structure, and magnetic properties of
naked and surface functionalized iron oxide Nanoparticles and their corresponding application
briefly discussed here
The surface of iron oxide Nanoparticles could be modified by organic materials or inorganic
materials, such as polymers, biomolecules, silica, metals, etc. These materials show many
interesting and unique properties with great potential for a number of technological appl ications. So
the past few years become fields of intense active research.
Generally, iron oxide nanoparticles are synthesized by a number of processes and often the
conditions of synthesis influence the structure and properties of these materials. Due to small
particle size of the nanoparticles their properties are very different from those of the materials in
the bulk. Similarly, a number of existing and new techniques have been developed which help in
doing an in depth characterization analysis of the materials synthesized by various methods. Most of
the analytical tools are common for different types of nanoparticles.
The unique properties of iron oxide nanoparticles allow the uses of several methods such as
Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM), Vibrating Sample
Magnetometer and four probe conductivity measurements specifically for studying their electrical
properties.

2.2

Synthesis of Iron Oxide Nanoparticles

The most common methods used for the synthesis of iron oxide Nanoparticles are: co-

precipitation, thermal

decomposition,

hydrothermal

synthesis,

Microemulsion,

sonochemical

synthesis, among of them the sonochemical synthetic route can all be directed to the synthesis of
high quality of iron ~xide nanoparti~les. In ~~dition, t~ese Nanoparti~les can als~__~!_prep~red!>Y~~~I:!_
.

17lpage

I~

other methods such as electrochemical synthesis, laser pyrolysistechniques, microorganism or

bacterial synthesis, etc. Here I am discussingabout the above methods and their examples.

2.2.1 Co-Precipitation
Co-precipitation is the most conventional method for obtaining Fe304 or Fe203. This
method consists of mixing ferric and ferrous ions in a 1:2 molar ratio in highly basic solutions at
room temperature or at elevated temperature. The size and shape of the iron oxide Nanoparticles
depends on the type of salt used (such as chlorides, sulfates, nitrates, per chlorates, etc.), the ferric
and ferrous ions ratio, the reaction temperature, the pH value, ionic strength of the media, and the
other reaction parameters (e.g. stirring rate, dropping speed of basic solution).
This method would critically affect the physical and chemical properties of the nanosized iron oxide particles. Generally, the saturation

magnetization

(MS) values found in

nanostructured materials are usuallysmaller than the corresponding bulk phase, provided that no
change in ionic configurations occurs. In addition, Fe304Nanoparticies are not very stable under
ambient conditions and are easily oxidized to Fe203or dissolved in an acidic medium. In order to
avoid the possible oxidation in the air, the synthesis of Fe304Nanoparticles must be done in an
anaerobic condition. Based on this point, Fe304Nanoparticles can also be utilized to prepare the
FeA Nanoparticles by oxidation or anneal treatment under oxygen atmosphere and oxidation is
not the important influence factor for Fe203 Nanoparticles due to its own chemical stability in
a!kaIine or acidic environment.
However, this method generates

particles with a wide particle size distribution, which

requires secondary size selection sometimes. A wide particle size distribution will result in a wide
range of blocking temperatures

(TB) due to T6 depends on particle size and, therefore non-ideal

magnetic behavior for many applications. In contrast, many recent publications have described
R;. M.

routes to obtain the monodispersed Nanoparticles,surfactants such as dextran or polyvinyl

L Ie.. (PVA) can be added in the reaction media, or the particles can be coated in a sub.sequent

step. Surfactants act as protecting agent for controlling particle size and stabilizing the colloidal
dispel5iolls. The disadvantage of these aqueous solution syntheses is that the high pH value of the
. -",,-.w- mixture has to be adjusted in both the synthesis and purification steps, and the process
~

, uniformed

and monodispersed Nanoparticles has only very limited success. On the other

__~~~vm",.~~~~~

~.'~m~~'

18 I P age

II

hand, wastewaters with very basic pH values are also generated in the experiment, which require
subsequent treatments for protecting the environment.

2.2.2 Thermal Decomposition

An organic solution phase decomposition route has been widely used in iron oxide Nanoparticles
synthesis, and decomposition of Fe(cuph (cup = N-nitrosophenylhydroxylamine),Fe(acach (acac =
acetylacetonate), or Fe(CO)s followed by oxidation can lead to high-quality monodispersed iron
oxide Nanoparticles, which usually requires relatively higher temperatures

and a complicated

operation.
With the smaller magnetite Nanoparticles as seeds, larger monodispersed

magnetite

Nanoparticles of up to 20 nm in diameter can be synthesized and dispersed into nonpolar solvent by

seed-mediated growth method. The process does not require a size-selection procedure and is
readily scaled up for mass production.
Although the thermal decomposition method has many advantages for producing highly
monodispersed particles with a narrow size distribution, it has the big disadvantage that the
resulting Nanoparticles are generally only dissolved in nonpolar solvents.

2.2.3

Microemulsion

Microemulsion is a thermodynamically stable isotropic dispersion of two immiscible phases (water

and oil) under the surfactant present, the surfactant molecules may form a monolayer at the
interface between the oil and water, with the hydrophobic tails of the surfactant molecules
dissolved in the oil phase and the hydrophilic head groups in the aqueous phase. In this sense,
Microemulsion and inverse micelles route can be employed for obtaining the shape and sizecontrolled iron oxide Nanoparticles.
Particularly, water-in-oil (w/o) Microemulsion formed by well-defined nano droplets of the
aqueous phase was dispersed by the assembly of surfactant molecules in a continuous oil phase.
Moreover, the results show that oleylamine act as precipitating and capping agent. However,
cyclohexylamine acts only as precipitating agent and does not avoid particle aggregation. Despite
the presence of surfactants, the aggregation of the produced Nanoparticles usually needs several
washing processes and further stabilization treatments.

19 I P age

2.2.4 Hydrothermal Synthesis

Iron oxide Nanoparticles with controlled size and shape are technologically important due
to strong correlation between these parameters and magnetic properties. The Microemulsion and
thermal decomposition methods usually lead to complicated process or require relatively high
temperatures. As an alternative, hydrothermal synthesis includes various wet chemical technologies
of crystallizing substance in a sealed container from the high temperature

aqueous solution

(generally in the range from 130 to 250 _C) at high vapor pressure (generally in the range from 0.3
to 4 MPa). This technique has also been used to grow dislocation-free single crystal particles, and
grains formed in this process could have a better crystallinity than those from other processes, so
hydrothermal synthesis is prone to obtain the highly crystalline iron oxide Nanoparticles.
It is suggested

that

the well-crystallized Fe304 grains formed

under

appropriate

hydrothermal conditions should be responsible for the increased saturation magnetization in nanosized~04.

The magnetic properties of the Nanoparticles exhibited a superparamagnetic behavior

at room temperature.

2.2.S Sonochemical Synthesis

As a competitive alternative, the sonochemical method has been extensively used to generate
ncJYeImaterials with unusual properties. The chemical effects of ultrasound arise from acoustic
cavitations, that is, the formation, growth, and implosive collapse of bubbles in liquid. The implosive
collapse of the bubble generates a localized hotspot through adiabatic compression or shock wave
formation within the gas phase of the collapsing bubble. The conditions formed in these hotspots
have been experimentally determined, with transient temperatures of 5000 K, pressures of 1800
atm, and cooling rates in excess of 1010 K/s. These extreme conditions were beneficial to form the
new phase, and have a shear effect for agglomeration, which is prone to prepare the highly
monodispersive Nanoparticles.
This method has been applied for the synthesis of various Nano composites, and. its versatility
has been successfully demonstrated

in iron oxide Nanoparticles preparation.

For instance,

magnetite Nanoparticles can be simply synthesized by sonication of iron (II) acetate in water under
an argon atmosphere.

The prepared

Fe304Nanoparticies are super paramagnetic

and its

magnetization at room temperature is very low (\1.25 emu g-l).

20

I Pa

ge

I
I

The five above mentioned synthetic methods have several advantages and disadvantages for
preparing iron oxide Nanoparticles, respectively. In terms of size and morphology control of the iron
oxide Nanoparticles, thermal decomposition and hydrothermal synthetic route seems the optimal
method.

For obtaining the water-soluble

and biocompatible

iron oxide Nanoparticles,

co-

precipitation often was employed, but this method presents low control of the particle shape, broad
distributions of sizes and aggregation of particles. As a time competitive alternative, sonochemical
route can also be used to synthesis iron oxide Nanoparticles with unusually magnetic properties.
Moreover, maghemite Nanoparticles show superparamagnetic

characteristics as expected.

Therefore, as the environmental protection and eco friendliness competitive alternative, green
chemistry and biological methods such as bacterially induced synthesis based synthesis of iron oxide
Nanoparticles are important advances.

21 I P age

2.3 Characterization Techniques

2.3.1 Fourier Transform Infrared Spectroscopy (FTIR)
The infrared spectroscopy provides a means of studying pure rotational, pure
vibrational and rotational

- vibrational

energy changes in the ground state of simple and complex

molecules. Infrared spectroscopy is mainly concerned with the absorption of energy by a molecule,
ion or radical from a continuum of radiation. The occurrence of vibrational transition in the infrared
regjon is dependent on an overall change of the electric dipole moment during the particular
vibration. The intensity of infrared spectrum is dependent on the magnitude of the dipole moment
change.
The infrared technique can be used to study gases, liquids, semi-solids, powders and
polymers. It is an information rich technique. The peak position, intensity width and the shapes in
the spectrum all provide useful information. It is a fast and easy technique in which the preparation
at the samples is easy and the results can be plotted in few minutes time.
Principle
The analysis of the IR spectroscopy is based on the fact that the molecules have specific
frequencies associated with the internal vibration of group of atoms. These frequencies generally lie
in the 4000 cm-1_200cm-1 region of the electromagnetic spectrum. When a sample is placed in a
beam of IR radiation, it absorbs radiation corresponding to the molecular vibration frequencies and
transmits all the other frequencies. Measurement of the frequencies of the absorbed radiation and

,I

the resulting plot of the absorbed intensity versus the frequency is called the IR spectrum of the

I~

material. Identification of the substances is possible because each chemical structure has a unique
IRspectrum, i.e., fingerprint of the material.
Instrumentation

For many decades Light dispersive sPE!ctrophotometer was used in the IR spectroscopy.
However, nowadays

it is superseded by the FOUrierTransform Infrared Spectrometer (FTIR).The

FTlRemploys an interferometer

in place of a monochromator. In the continuous scan mode the

,~"~~".~~-~~~.,'

~~_.~,~
22 I P age

,
I:

II

moving mirror is repetitively scanned fast to generate the Fourier transform of the IR spectrum.
After the co-addition of many scans, to reduce the signal to noise ratio, the Fourier transform is
\

converted t(1 the IR spectrum by a dedicated computer. The IR spectra of the samples were
recorded u;ing Shimadzu FTIR model 8101A in the KBr medium in the range 4600 cm-I_
The components of the 8101 A FTIRspectrophotometer

400 em-I.

are given below.

Spectrophotometer Unit
The spectrophotometer

unit measures the infrared absorption spectrum of the sample. It

consists of source, interferometer, sample compartment and a detector.

1. Source- The FTIR8101 series spectrophotometer

has a SiC heating element (Globar) as the IR

source.
2. Interferometer-

The spectrophotometer

is equipped with Michelson Interferometer,

which

interferes with the infrared light emitted from the source and produces the interferrogram.

3. Sample Compartment- A sample is put in the compartment, which employs a sample holder on
which either a film or a pellet of the material mixed with KBr is used.
4. Detector- The spectrophotometer

uses the Deuterated triglyceride

sulfide (DLATGS) as a

detector. It is a sensitive pyroelectric detector operating on the principle of the "pyroelectric effect".

Centro/Unit
The control unit of the FTIR 8101 series carries out operations for measurements, data
processing and spectral output. It incorporates a CPU system, a high-speed arithmetic processor, a
floppy drive, etc. The CPU controls and makes the measurements and Data processing. The
arithmetic processor makes the Fourier transform of the interferrogram to a spectrum and carry out
the

data

processing. The floppy

spectrophotometer

disk saves and manages the

measured

spectra.

The

is equipped with a printer with the help of which we get the spectra in the

plotted form. (Graph between %T and wave number em-I). It is also possible to get the hard copy of
spectral data for its further processing.

23 I P age

Control

unit

Spect:rophoto2Deter

~I
I

unit

System Configuration of the FTIR

;;.:

::,~~t:~J~
Q).~.....

.'.'~ ~"

...

'.

tt~=-IQCJ'Qd.,;'1Ia)

..,. JP#i;~~..,,~~

Q~o t4..t~._

U' II.~,.. wi:1!IiitOr

,. ~_:ipIat'

.. Jf..N.~~;
o $~"'~.
.~H(8"'~J~'J!IIqur

":'

Optical Imaging through the FTIR

24 I Page

l
2.3.2 Powdered X-Ray Diffraction
We know that in solid crystalline materials the atoms are arranged in a regular

pattern in three dimensions. Repeating a certain basic unit of structure having minimum volume,
called as the unit cell, can make the whole crystal. A unit cell may be described

by the lengths of its

sides (a, b and c) called as lattice parameters.

In a crystal lattice there are several sets of parallel planes possible. Each set of
parallel planes is uniquely described by three integral co-ordinates (h k I) called as the Miller indices.

The example of such parallel planes in case of cubic structure is as (111), (200), (311), (220), (222),
(4OO),(440), (333), (444), etc.
Bragg's Law

Crystalline materials act as three-dimensional diffraction gratings for the X-rays due
to the inter-atomic distances of the order of Awhich are comparable to the wavelength of X-rays.
When a beam of X-ray is incident on a crystalline sample, the scattering of the X-rays takes place
from atoms of the sample. If the scattered beams are in phase they interfere in a constructive
manner and we get maximum intensity in that direction. It is recorded in the form of an arc of circle

in the case of Scherrer method or in the form of a peak in the modern X-raydiffractometer. The
planes from whichthe X-raysare scattered are calledas the "reflecting planes".

X-Ray diffraction from the crystal

25 I P age

Bragg in 1913 derived a formula, which relates the wavelength of the X-ray to the spacing of
the atomic planes and the angle of diffraction:-

2dsin8

= nl

Where
d = spacing between the parallel planes
a = angle of Diffraction
n = order of diffraction
A. = wavelength of X-ray

Experimental Set-up
X-ray diffraction is a powerful tool to obtain information about the crystal structure,
composition, phase, particle size, lattice strain, lattice constants, nature of crystalline materials
(poly/single), lattice defects, etc. There are three methods used in the X-ray diffraction.
i)

Laue Method

ii)

Rotating Crystal Method

iii)

Powder Method

All these methods are based on the Bragg's law of diffraction. In the Laue's method, a beam
of continuous X-ray is used while keeping the angle of incidence fixed. It is used for the study of
single aystal. The rotating crystal method is also used for single crystals. In this method a
monochromatic beam of X-ray is incident normally on a single crystal, which is rotated about a
certain direction. For a particular angle when the Bragg's condition for diffraction

is satisfied,

reflection of X-ray is observed. This method is very useful in the field of X-ray crystallography.

The

powder diffraction method is used for the study of polycrystalline materials in which different
aystallites

of materials are randomly oriented in all directions. In this method the incident

monochromatic

radiation strikes a finely powdered specimen or a fine-grained polycrystalline

specimen kept in a sample holder of the diffractometer.

Each particle of the powder is a tiny crystal

oriented at random with respect to the incident beam. The particles will be oriented in such a way
that different sets of parallel planes will satisfy the condition of Bragg's diffraction. The result is that
every set of lattice planes will be capable of reflection. The diffraction pattern has the form of a
cone for a set of parallel planes. For each set of planes there will be a separate cone. In the earlier
times the Debye-Scherrer Cameras were being used to observe the diffraction pattern. In this
method a narrow strip of film is mounted into a short cylinder with the specimen placed on its axes
IPage

-,:

"

,
I

:1

and the incident beam directed at angle to this axes. The cone of diffracted radiation intersects the
cylindrical strip of the film in lines. When the strip is unrolled and laid out flat, the resulting pattern
has the appearance of the circular arcs. By measuring the position of a given diffraction line on the

film, 6 can be determined, and knowing A.we can calculate the d spacing of the set of planes.
I

Nowadays, the X-ray diffractometer is used as a tool in the diffraction analysis. This
instrument is known as a diffractometer when it is used with X-rays of known wavelength to
determine

the

unknown

spacing of crystal planes. There are four components

of the

diffractometer:i)

X-raySource

ii)

Specimen

iii)

Optics

iv)

X-ray detector
All these components lie on the circumference of a circle known as focusing circle.

The angle between the plane of the specimen and the X-ray source is6, known as Bragg's angle. The
angle between the projection of X-ray and the detector is 26. The diffraction pattern produced with
the geometry is called as (8-28) scan. In this geometry the X-ray source is fixed and the detector
moves through a range of angles. The 28 measurement range is typically from 0 to 170. The
central component of the X-ray diffractometer is called goniometer and contains the specimen
holder. It has arms to which the X-raysource and the detector are mounted.
X-ray Source:

The mainly used X-ray sources are:-

S. No.

Source

Energy (KeV)

Wavelength (A)

1.

Molybdenum

50 - 55

0.7909

2.

Copper

25 - 40

1.5405

3.

Iron

25 - 30

1.9360

Chromium

25

2.2897

4.

--~~,"~~-~-

--.......

~-~~,-~

27

I P age

Copper is the most frequently used target and we have used it in our experiments (1.5405 A).
Specimen
In a typical X-'raydiffraction experiment the specimen should contain numerous small
grains of size ~ 50 11m(325 -mesh sieve). The quantity of the sample should be quite small ranging
from few milligrams to few grams.
Optics
On the X-ray source side a line beam of X-ray passes through a series of slits called soller
slits. These slits consist of a series of closely spaced parallel metal plates that defines and collimates
the incident beam. These slits are usually made up of metals with high atomic numbers such as
molybdenum or tantalum.
Detector
Mainly, the following three types of X-ray detectors

are used in the modern

diffractometers. They are:

a)

Proportional Counters

b)

Scintillation Counters

c)

Solid State Detectors

In the above the gas proportional counter and scintillation detectors are most commonly
used. The modern X-ray diffractometer systems are equipped with a computer interface by which it
can be connected to a personal computer. All its functions can then be controlled by the computer
system. the software automatically calculates the d

- values

of the peak intensities, relative

intensity, full width at half-maximum, etc. The graph between the intensity and the angle of
diffraction (2e) of the peaks can also be plotted.

._~_._~_VAVA_~_A~.m~~

_c~~~_~v___

28 I P age

tion ~

Schematic Diagram of Powder x- Ray Diffractometer

Information from X-ray diffraction

Identification of Phases

After recording the X-ray diffraction pattern for a material, the first step involves the
indexing of the XRDpeaks. The indexing means assigning the correct Miller indices to each peak of
the diffraction pattern. The correct indexing is done only when all the peaks in the diffraction
pattern are accounted for and no peaks expected for a structure is missing from the diffraction
pattern. There are three ways in which one can index the diffraction pattern:-

Comparing the XRD pattern with the Standard Data (JCPDS cards)

a)

Analytical methods

b)

Graphical Methods

'~W__A~.

~'~_"_~~~'A~~~~--~-"-~~-

'~"""~~"C~~~,~_._,.~_~~.~_~~A~~~~'"W'~'''

29

I P age

In our experiments, we have used the first method to index the XRDpattern and
accordingly the phase ,of the material was identified. Most of the samples have the cubic or
hexagonal structure. ThE'selections rules for these are:Calculation of lattice Parameters:-

S.No.

Crystal Type

ReDectionPresent

Simple Cubic

A...v" ...I

BodyCentered Cuble

h+ktI k even

Face Centered Cuble

II,k,Ian 1IIIIIIhed
(Ei0le1' aD odd 01'aD even)

h+2k=3Nwhen lis even

4

h+2k=3Nwhen lis odd

Heugonal
h+2k=3N:J:1when lis odd
h+2k=3N:I:1when lis even
Selections

Rules for Cubic and Hexagonal Crystal Systems

After indexing the diffraction pattern, the type of the Bravais lattice is identified from the
relation between the d-values, miller indices and the lattice parameters of the cubic crystal

d=

a
~ 1t'J. + kZ + (l.

Where
d
=
d-value of the peak
h, k, 1 =
Millerindicesof the peak
a
= lattice parameter
Sincefor a peak of known plane (h, k, I),d-value is known.So 'a' can be calculated.

30 I P age

..

t;

For a Tetragonal system

h2 +k2

d2 Let
1
d2

Z2
+-

a2

C2

h2 + k2 = Mi'

= Di.

Z2 = Ni

And

1
-c
~C

~=A.
a

The equation reduces to

il
I
II

jl

M1A+N1C=D1

A similar equation is also formed for another peak

M2A+N2C=D

Then the two equations are solved simultaneously for A and C and then the values of 'a' and I c' are

III

obtained.

For Hexagonal system

4 h2 +h.k+12

d2 ="3(

a2

[2

)+

c2

Similar to tetragonal system, two peaks are considered and two equations are solved
simultaneously to calculate the values of a and c, respectively.

For Orthorhombic system

1

h2

-=-+-+d2
a2

[2

b2

c2

In this system three peaks are considered

and three

equations

are solved

simultaneously to obtain the values of a, band c, respectively.

~~"-""""~-~~~"-~-~'.,'~~~

31 I P age

\i

2.3.3 Vibrating Sample Magnetometer (VSM)

The Vibrat ng Sample Magnetometer

(VSM) is the basic instrument for characterizing

magnetic materiais. Since its invention some forty years ago, it has become the workhorse in both
laboratory and production environments for measuring the basic magnetic properties of materials
as a function of magnetic field and temperature. Computer control and automation was introduced
to the VSM two decades ago, but otherwise there have been no major advancements

in

performance until quite recently. This quantum improvement in performance has been imposed by

Iii
HI

the advancements in magnetic recording storage systems and, more specifically, by the advanced
magneto-resistive and spin valve heads and the high coercivity and low remanence thickness
product media employed in these systems. The magnetic layer(s) in these advanced heads and
media have very low magnetic moment per unit area, requiring significantly improved sensitivity

Ii~
If::i

and high signal-to -noise ratio magnetic metrology tools.

I
II'

Principle
It'
ili

Avibrating sample magnetometer (VSM)operates on Faraday's law of Induction, which tells

us that a changing magnetic field will produce an electric field. This electric field can be measured

ii,
II~
11

and can tell us information about the changing magnetic field. A VSM is used to measure the

II
II
'1
Ii

magnetic behavior of magnetic materials.

II
iI:

Experi~ntalsetup
Magnetic measurements

of our samples at room temperature

were carried out by ADE

model EV-S VibratingSample Magnetometer (VSM).A VSMoperates by first placingthe sample to

be studied in a constant magnetic field. If the sample is magnetic, this constant magnetic field
magnetizes the sample by aligning the magnetic domains, or the individual magnetic spins, with the
field. The stronger the constant field, the larger the magnetization will be observed. The magnetic
cr&pOle
moment of the sample creates a magnetic field around the sample, sometimes called the
magnetic stray field. As the sample is moved up and down, this magnetic stray field is changing as a
.

functionof time and can be sensed by a set of pick-upcoils.The alternating magneticfield causes an
electric field in the pick-up coils according to Faraday's law of Induction. This current is proportional
to the magnetization of the sample. The greater is the magnetization, the greater the induced

32

I Page

,It
I"
!

II~

'I

current. The induction current is amplified by a Trans -impedance amplifier and lock-in amplifier.
The various components are hooked up to a computer interface.
The VSMconsists of ten parts:

vibration exciter and sample holder (with angle indicator)

sensor coils

Hall probe

amplifier

control chassis

.
.
.

lock in amplifier

water cooled electromagnet and. power supply

meter
computer interface

Water cooled electromagnet and power supply

The water cooled electromagnet, along with the power supply, generates the constant
magnetic field used to magnetize the sample.
Vibration exciter and sample holder (with angle indicator)
The sample holder rod is attached to the vibration exciter, and the end of it hangs down in
between the pole pieces. The exciter moves the sample up and down at a set frequency, typically
85Hz. The sample rod can be rotated to achieve the desired orientation of the sample to the
constant magnetic field. There are also three knobs for controlling the x, y, and z positions of the
sample.
Sensor coils
The sample produces an alternating current in these coils at the same frequency as the
vibration of the sample. The signal generated contains the information about the magnetization of
the sample.
Amplifier
The amplifier does just that

-amplifies the signal created

by the sensor coils.

Control chassis
This controls the 75Hz oscillation of the exciter.
"~_,,".__~A"~~,~~"

33 I P age

lock in amplifier
This amplifieris tuned to pickup only signalsat the vibratingfrequency.Thiseliminates noise
from the environment, such as from the overhead lights or hovering spacecraft nearby (unless the
noise happe~s to be an 85Hz signal).

Meter
This is used to measure some important things.

Computer Interface
The software makes data collection easier by automating the control of the various
components during data collection. The data can be graphed and plotted on the printer.
The VSM, shown schematically in the Figure, employs an electromagnet which provides the
magnetizing field (DC), a vibrator mechanism to vibrate the sample in the magnetic field, and
detection coils which generate the signal voltage due to the changing flux emanating from the
vibrating sample. The output measurement displays the magnetic moment M as a function of the
field H.

Schematic Diagram of Vibrating Sample Magnetometer (VSM):-

Vibration

unit

"

,-~~--_.

34 I P ag e

2.4 PrE'~paration of Fe304 by Co-Precipitation

2.4.1 Introduction
Iron oxides (either Fe304or yFe203) are usually prepared by an aging stoichiometric mixture
of ferrous and ferric salts in aqueous medium. The chemical reaction of Fe304 formation may be
written as eq 1.
Fe2++ 2Fe3++ SOH-- Fe304+ 4H20

(1)

According to the thermal dynamics of this reaction, complete precipitation of Fe304should

be expected at a pH between Sand 14, with a stoichiometric ratio of 2:1 (Fe3+jFe2+)in a nonoxidizing oxygen environment.
However, magnetic Fe304is not very stable and is sensitive to oxidation but Magnetite
(VFe203)in the presence of oxygen can be formed. Oxidation in air is not the only way to transform
magnetite (Fe304) in to maghemite (yFe203)' Various electron and ion transfer depending upon the
pH of the suspension are involved, according to eq 2.
Fe304+ 2H+- yFe203 + Fe2++ 2H20

(2)

The main advantage of the co-precipitation process is that a large amount of nanoparticles
can be synthesized. However, the control of particle size distribution is limited, because only kinetic
factors are controlling the growth of the crystal. In the co-precipitation

process, two stages are

involved: a short burst of nucleation occurs when the concentration of the species reaches critical

super saturation, and then, there is a slow growth of the nuclei by diffusion of the solutes to the
surface of the crystal. To produce monodispersed iron oxide nanoparticles, these two stages should
be separated; i.e., nucleation should be avoided during the period of growth.
Here I had reported the co-precipitation method for the synthesis of iron oxide nanoparticles
in aqueous solution in the presence of NaOHjNH40H. Their characteristics were compared with
iron-oxide

nanoparticles.

The

samples

were

investigated

by

Fourier

Transform

Infrared

Spectroscopy (FTIR),X -Ray Diffraction (XRD) and Vibrating Sample Magnetometer (VSM).

351 P age

II
Ii
!i
t
1I

2.4.2 Experimental
Materias
Ferrous chloride tetra hydrate (FeCI2'4H20), ferric chloride anhydrous (FeCh) and sodium hydroxide
(NaOH) and Ammonium Hydroxide (NH40H) were purchased from Fluca (Merck). These reagents were used
directly as received. De-ionized (MiIIi-pore) water was used in the synthesis of nanoparticles, and in the
rinsing of clusters.
Synthesis of iron-oxide nanoparticles
Ferrous chloride tetra hydrate (FeCI2'4H20) and ferric chloride anhydrous (FeCI3)were mixed at room
temperature (Fe2+/Fe3+= ~). The co-precipitation of iron oxide nanoparticles was carried out in a reaction
with magnetic stirring, by slowly adding 1.5 M NaOH or Ammonium Hydroxide (NH40H)until obtaining pH 9
to 12/ pH= 10 to 12 at room temperature (see Schematic Diagram) then precipitate was magnetically
separated from the supernatant and washed several times with distilled water, until obtaining pH 7. During

I.

II
I'
~.
!~'

each washing step, samples were separated from the supernatant using a permanent magnet. Thoroughly

washed magnetic particles were dried at room temperature, yielding a fine powder.

COmprecipitation

Black Precipitate Formed

Schematic Diagram of Fe304 Preparation

PhysicaJ Measurements
The structural characterization of the samples was carried out by power X-ray diffraction (XRD)performed
DOa Phiips X' Pert Pro system by using Cu Kal(?= 1.54060 AO)radiation. The Fourier transform infrared (FTIR)
spectra have been recorded in KBr by using FTIRspectrometer Model Shmadzu DR- 8101A NT-MDTsolver

P'aO. Room temperature magnetic measurements were carried out by ADEmodal EV-5 Vibrating Sample
Mai2neCnmeter (VSM).

.~~~_W_~'A~~'

36 I P age

3.Result and Discussion

FllR Studies
The FTIR

spectra of synthesized

samples of Fe304 Nanoparticles

1

magnetite

were prepared

particles

have been

shown

in the below

at varying PH of 9 to 12. A broad and intense peak

figure.

Four

3425 cm-

and a small intensity band at -1636cm-1 correspond to stretching and bending modes of vibration of

hydroxyl

groups respectively. All synthesized magnetic nanoparticles show vibration band at -580cm-1and

400 cm-1 associated

characteristics

with the stretching

and tensional vibration modes of the magnetite

peaks confirm the formation

of magnetite

Fe -0 bonds.

These

phase. It is also clear from the following graph that

on increasing the PH value, the Peak of Fe-O bond stretching is intensified.

IT
39,00

]I

2U6

e..:.

".woo
,9

31100,9

'1500.9

'toou

c.-l

Figure: FTIRspectra of the synthesized magnetic particles with different pH through NaOH

.~~c~~_,~_.w_~~.~,~~,.~~~w..,~~~-,~-~,

37 I P age

I.
!'I

The FTIR spectra

figure.

Three

peak

samples

of synthesized

of Fe304 Nanoparticles

3425 cm-1 and a small intensity

vibration

of hydroxyl

~580cm-land
bonds.
following

groups

characteristics

were prepared

All synthesized

with the stretching

peaks

graph that on increasing

particles through

NH40Hhave been shown in the below

at varying

band at ~1636cm-1 correspond

respectively.

400 cm-l associated

These

magnetite

confirm

magnetic

and tensional

the formation

pH of 10 to 12. A broad

to stretching
nanoparticles

vibration

of magnetite

phase.

the pH value, the Peak of Fe-O bond stretching

and bending modes of

show

modes

II

and intense

vibration

band

of the magnetite
It is also clear

at

Fe-o
from

,
'Ii
I.'

the

is intensified.

n
46.00

49.

~....

~
38.

39.88

~.

29.00

18.

18.00

1.

..8

,
i
4009.8

1.00
!

3900.8

499.9

1000.9

2eoo .9

tt-1
Figure: FTIR Spectra of the synthesized magnetic particles with different pH by NH40H.

--~-~_.

38

I P age

XRD Studies
The followi ng.data has been obtained from the XRD analysis of the sample prepared:

D (0A)

Intensity

2.9578
2.5233
2.0897
1.6124

999
361
294
274

3
4
2
3

1
4
2
3

1
0
0
0

Figure 1 shows the XRDpattern of Fe304Nanoparticles.This data was matching with the ICSD
document no. 821533 which confirms the presence of Fe304 in the prepared sample, the mineral
name according to the document is Magnetite. The phase of the nanoparticles obtained was Cubic
and the lattice obtained was Face Centered.
CoIriS1OOO

..

Fe204jlaOI'UO.xnimI

.,...
~

...

S
U\-

-~

',0

12.

fa
....

fR

'f'
;-.t-

500

,.
20

.90

40
p()~~j!ll\~}

70

Figure 1. XRDPattern of Fe304 Powder of pH=10 from NaOH

,~~--,-,~,'-~,~

391

P age

2500

2()00

1500

1000
5

'to 15

20

2~5 30

35

XRDGrapho~Fe304

40 45
5'0 5:5 60
rtlcl.. of.Ph-10 _Ith NeOH

65

70

75

80

85

2500

2000

1500

1000

1-0

15

20
X~D.G

2530
ph of Fe3Q4

3.5

4'0
pent.,I..

45
50
55
60
of _-11
wwhh NaOH

65

70

75.

80

85

250()

2000

1500

10PO

1016

20
25
303p
XRD Grilphof FeS04

55 ao 65 70

40455'0
pIIr:tkIes

of Ph-12

with

7?1 80 85

N.OH

_m~m_~~'~..o_"",',~,'~__,>,,_~~

40lPage

2500

2000

1500

1000

10

15:2'0

25'
30
35
40
XRD Grilph 'of "a304 :partldes

4.5

5d

55

of Ph-10with

60

65

70

75

8.0

85

NH3

2500

2000

1500

1000

10

15

20

25
30
35
XRO Graph ~f Fa_

40
45.
50
partlc:'_
ot'.Ph-11

55
_Ith

6Q
NH3

65

70

75

so

S5

2500

2000

.. 500

1000

10

15

2'0
25
XRDGrilph

30
3540
of l=a304 particles

4550
of Ph-11.~S

55
6065
wl~h N~

7'0

75

,80

8'5

Figures of X-ray powder diffraction patterns of the synthesized magnetic particles

41 I P age

-~,-"

----._-

I'

Below table and graph shows the Particle Size of the Iron-Oxide Nanoparticles prepared from
different alkali solvents. XRDData Analysis of Fe304 Samples obtained from Particle Size Analyzer
are:-

~~~-rnmhtI..

~~1

pH = 10

NH3

10nm

pH = 11

NH3

9nm

pH = 12

NH3

8.5 nm

pH = 10

NaOH

9.5nm

pH = 11

NaOH

9nm

pH = 12

NaOH

7 nm

. . . . . . . . .. .. .. .. .. .. . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . ..................
. . . . . . .
. .. . .. . .. . .. . .. . .. . .. . .. . .. .
............... ....
... .... .. .. . . . .
. . . . . . .. .. . . . . .. .. .
............. ......
............... ....
. .. . .. . .. . .. . .. . .. . . . . . . .
.... ...... ... . . .
............ . . .

"12.

"10.

'S':
I.
'6

:-:.~:
. . . . . . . . NH:3:-:
.. . . .

"

'.'~.NaOI:-I".

. .. . .. . .. . .. . .. . .. . .. . .. . .. .
. . . . . . . . .
...................

. . ....... .......

. .. . .. . .. . .. . .. . .. . .. . .. . .. .

............ ... ....

.. .. . ... . .. . . .. .. ..
............. ......

...................
. . . . . . . . . .

t. . . . . . . . . . . . . .'
:1~ : . : . : .:

..

. . . ~'.'.'.'.'.'.'.'.'.

. . . . . . ):~. : . : . : . : . : . : . : . : . : . : . : . : . : . : . : .
:H. : . : . : . : . : . : . : : : ..............
:
:
. . . . . . .
. . . . . . . . . . . . . . "

:":.:.:.:.:.:.:.

x-v axis showing pH and Particle Size [nm] respectively

42 I P age

VSM Studies
Figures given below are tt e magnetization curve for coated synthesized nanoparticles at
room temperature. It can be seen that th,e 'magnetization curve shows very small coercivity and remanence.
This observations reveal that a significant number of Fe304nanoparticles have particles size above the critical
size for superparamagnetic behavior.

~
...

...

4'H~
1
-t1&:tI 1ft...

:: I :,:

nZlli

......

.....
"'"

-as:... ! SGI[~

-~ID !; ...-

! llR

iCCBiItrM!F.iIIrI....MJM

J4mo1
aM-I

,..

...

~-"~~M"iW

~1ItMI
om,j1+Ui1:1I.....m)

VSM Graph of Magnetic

..
.....

...
....,
""'.
...
L'II

NanoparticJes

of pH=10,11

""
."".
'"'
""

and 12 of NH40H and pH=12 of NH3

'

'_~~_'_~'~,,"N~",~'~"",~'_~

43

I P age

CONCLUSION

Synthesized iron oxide nanoparticles or magnetite through a simple and effective

method in which the nanoparticles are stable and water dispersible. Formation of pure magnetite phase
observed from XRDStandards. The preparing process of Fe304 nanoparticles is facile and possible to scale up.
The average crystallite size is found to be nearly

7 nm. Non-destructive determination of size and size

distribution from XRDdata has two advantages over microscopy: firstly, the much larger number of particles
probed in one measurement, and secondly, the absence of 'barred', i.e. inaccessible, particles, which often
compose the greater part of the sample for microscopy, since microscopy techniques are surface-sensitive.
VSM graph confirms their Superparamagnetic

behavior. The presence iron oxide nanoparticles are also

confirmed from FTIRspectroscopy.

441page

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