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MAGNETIC NANOCOMPOSITES
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Contents
Department of Mechanical EngineeringPage 1
1.
2.
3.
4.
5.
6.
7.
8.
Introduction
Brief History
Magnetic Properties
Types of MNC
Synthesis
Applications
Conclusion
References
3
4
6
10
14
18
22
23
CHAPTER I
INTRODUCTION
Materials with features on the scale of nanometer often have properties dramatically different
from their bulk scale counterparts. Nanocrystalline materials are single phase or multiphase
Department of Mechanical EngineeringPage 2
polycrystals, the crystal size of which is of the order of few nanometers so that about 40 to 80
% of the atoms are in the grain boundaries [1]. Nanostructure science and technology is a
broad and interdisciplinary area of research and development activity that has been growing
worldwide in the past decades. Important among these nanoscale materials are
nanocomposites, in which the constituents are mixed at nanometer length scale. They often
have properties that are different compared to conventional micro scale composites and can
be synthesized using simple and inexpensive techniques. The study of nanocomposite
materials requires a multidisciplinary approach with impressive technological promise,
involving novel synthesis techniques and an understanding of physics and surface science.
During the last decade, the development of magnetic nanocomposite materials has been the
source of discovery of spectacular new phenomena, with potential applications in the fields of
information technology, telecommunication or medicine. Magnetic nanocomposite materials
are generally composed of ferromagnetic particles (grain size in nanometer scale) distributed
either in a non-magnetic or magnetic matrix. The shape, size and distribution of the magnetic
particles play an important role in determining the properties of such materials [2]. The
matrix phase separates the magnetic particles and changes the magnetic exchange interaction.
This affects the transport and magnetic properties. Therefore, understanding and controlling
the structure of materials is essential to obtain desired physical properties.
CHAPTER II
BRIEF HISTORY
Nanocomposite magnetic materials have their origins in the amorphous alloys that were
brought to market in the 1970's. Amorphous materials are characterized by a lack of long
range atomic order, similar to that of the liquid state. Production techniques include rapid
quenching from the melt and physical vapour deposition is another. The lack of crystallinity
causes amorphous materials to have a very low magnetic anisotropy. METGLAS 2605
Fe78Si13B9 is a common amorphous magnetic alloy, in which B acts as a glass forming
element. The importance of anisotropy suggests searching for other materials with isotropic
magnetic properties. In magnetic materials the ferromagnetic exchange length expresses the
characteristic distance over which a magnetic atom influences it's environment, and has
values on the order of 100 nm. If the magnet has a structure with grain diameters smaller than
the exchange length, it becomes possible to "average" the anisotropy of the grains to a low
bulk value. Such a material then realizes the high saturation magnetisation (Ms) of the
crystalline state and low coercivity (Hc) due to randomized anisotropy.
In 1988 Y.Yoshizawa [3] developed the FINEMET alloy based on Fe73.5
Si13.5B9Nb3Cu1. This was an extension of the common Fe-Si-B alloy with Cu as a
nucleation agent and Nb as a grain refiner. The material is produced in the amorphous state
and then crystallized by annealing. Nb that segregates to the grain boundaries acts a diffusion
barrier preventing grain growth. The structure is a nanocomposite of 10- 100 nm diameter
bcc- FeSi grains embedded in an amorphous intergranular matrix.
In 1990 K.Suzuki [4] reported the development of the Fe88Zr7B4Cu1 alloy which was
named NANOPERM. Zr and B act as glass forming agents in this alloy and the
microstructure consists of -Fe grains embedded in an amorphous matrix. By eliminating Si,
higher saturation inductions are achieved than in FINEMET, but the Hc are also higher. The
amorphous intergranular phase in both FINEMET and NANOPERM have Curie temperatures
lower than that of the nanocrystalline grains.
In 1998 M.A. Willard [5] reported the development of HITPERM, an alloy based on the
composition Fe44Co44Zr7B4Cu1. The key distinction is the substitution of Co for Fe.
HITPERM forms '- FeCo grains in a Co enriched amorphous matrix. The amorphous matrix
has a Curie temperature higher than the primary crystallization temperature of the alloy. This
allows the '-FeCo grains to remain exchange coupled at high operating temperatures. Due to
the presence of Co, HITPERM alloy has an Ms higher than FINEMET or NANOPERM as
well as a higher Hc.
CHAPTER III
MAGNETIC PROPERTIES OF NANOMATERIALS
The effect of reducing the physical size of materials is of great importance
from both
fundamental considerations and modern practice. A brief discussion of
magnetic behavior of
low dimensional systems is focused based on literature. Magnetic
nanoparticles exhibit specific properties such as coercivity and
superparamagnetism, generally attributed to reduced dimensions.
3.1 Coercivity
The coercivity of fine particles has a striking dependence on their size. Fig.
1 shows
very schematically, how the size range is divided, in relation to the
variation of coercivity
with particle radius r.
domain behavior (SD) between r0 and the single domain limit rc; and multidomain
behavior (MD) for r > rc.
The two curves zero field cooled (ZFC) and field cooled (FC) show different
behavior
CHAPTER IV
TYPES OF MAGNETIC NANOCOMPOSITES
4.1 Ceramic-matrix nanocomposites
In this group of composites the main part of the volume is occupied by
a ceramic, i.e. a chemical compound from the group of oxides, nitrides,
borides, silicides etc.. In most cases, ceramic-matrix nanocomposites
encompass a metal as the second component. Ideally both components,
the metallic one and the ceramic one, are finely dispersed in each other in
order to elicit the particular nanoscopic properties. Nanocomposite from
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are absent in the unfilled matrices. This effectively changes the nature of
the original matrix (such composite materials can be better described by
the term genuine nanocomposites or hybrids ). Some examples of
such new properties are fire resistance or flame retardancy, and
accelerated biodegradability.
In a recent study, polymeric nanocomposites were fabricated using
various one-dimensional carbon nanostructures such as single- and multiwalled carbon nanotubes, as well as two-dimensional carbon and
inorganic nanomaterials such as graphene platelets, graphene
nanoribbon, single- and multi- walled graphene oxide nanoribbons,
graphene oxide nanoplatelets and molybdenum disulfide nanoplatelets as
reinforcing agents, to improve the mechanical properties of
poly(propylene fumarate) nanocomposites, for bone tissue engineering
applications. Significant mechanical reinforcement (i.e. increases in the
Young's modulus, compressive yield strength, flexural modulus and
flexural yield strength) were observed at low loading concentrations (0.010.2 wt%) of nanomaterials. The results suggest that mechanical
reinforcement is dependent on the nanostructure morphology, defects,
dispersion of nanomaterials in the polymer matrix, and the cross-linking
density of the polymer. In general, two-dimensional nanostructures can
reinforce the polymer better than one-dimensional nanostructures, and
inorganic nanomaterials are better reinforcing agents than carbon based
nanomaterials. In addition to mechanical properties, multi-walled carbon
nanotubes based polymer nanocomposites have also been used for the
enhancement of the electrical conductivity.
CHAPTER V
SYNTHESIS OF MAGNETIC NANOCOMPOSITES
In the field of magnetic nanocomposites, there has been a lot of progress in the preparation of
functional magnetic nanocomposites and hybrid materials. Some of the latest magnetic
nanocomposite materials will be briefly explained. The preparation methods, few properties
and applications will be explained in short since there are a lot of new and hybrid materials.
The main focus will be on the different types of the functional nanocomposites and hybrid
materials. There are a number of categories according to which functional nanocomposites
are classified. Some of them that will be dealt with are given below
The combination of two nanoscaled entities into a single hybrid particle has recently attracted
much attention due to the numerous possibilities of application. Hybrid NPs may provide a
platform with dual imaging capabilities for medical diagnosis (e.g., simultaneous magnetic
and optical imaging), dual action combining magnetic imaging and therapy, and multiplexing
in sensors. By this approach, the respective properties of the components may be combined
and optimized independently. In addition, cooperatively enhanced performances due to
collective interactions between the constituents have been achieved. Otherwise, however, the
direct combination of the different entities may lead to undesired effects such as
luminescence quenching by direct contact of magnetic NPs and quantum dots (QDs). To date,
several morphologies of multicomponent, magnetic hybrid NPs have been reported, including
coreshell and heterodimeric NPs.
The general strategy for multicomponent nanostructures is to first prepare NPs of one
material, and then use them as nucleation seeds to deposit the other material. This strategy
has been well established for the synthesis of semiconductor QDs with epitaxial shells, while
the controlled synthesis of uniform NPs that combine materials with different
crystallographic structures, lattice dimensions, chemical stabilities and reactivities still faces
many challenges. To date, a number of heterostructures has been synthesized by applying a
seedmediated approach. Coating has been routinely applied for magnetic core stabilization
and surface functionalization in view of biomedical and technical applications.
One of the simplest methods for preparing coreshell type NPs has been the partial oxidation
of magnetic metal NPs to form a shell of the native oxide on the particle surface.
Polycrystalline Fe3O4 shells, e.g., which were generated by chemical oxidation on Fe
particles, were shown to successfully protect and stabilize Fe NPs against full oxidation.For
Co-CoO NPs, additionally to their stabilization, an exchange bias effect was observed as a
result of a strong interaction between the nanometre scale antiferromagnetic CoO layer and
the ferromagnetic Co core. Bimagnetic coreshell systems such as FePt-Fe3O4 or FePtCoFe2O4, where both core and shell are strongly magnetic (ferro- or ferrimagnetic), show
effective exchange coupling phenomena and facilitate the fabrication of magnetic materials
with tunable properties. The magnetic properties, e.g., magnetization and coercivity, can be
readily controlled by tuning the chemical composition and the geometrical parameters of the
core and the shell (Fig. 3).
Fig. 3: FePt-Fe3O4 NP assembly: (a) TEM image, (b) magnetization curve measured at 10 K (Fe3O4 shell
thickness 1 nm), and (c) normalized coercivity hc as a function of the Fe3O4 volume fraction.
Fig. 4: Schematic illustration of a typical four-step procedure for the synthesis of superparamagnetic
mesoporous SiO2 spheres.
After obtaining Fe3O4-SiO2 particles, by adding other compounds, it can be used in various
Biomedical applications Some of them are given below
The Fe3O4- SiO2 particles could be further loaded with fluorescing dyes (fluorescein
isothiocyanate (FITC) and rhodamine B isothiocyanate (RITC)) and doxorubicin
(DOX) and were tested for MR and fluorescence imaging as shown in figure 5(a).
Fig. 5(a): Uniform Fe3O4-SiO2 particles with a single Fe3O4 core [9]
2-bromo-2-methylpropionic acid-modified Fe3O4 NPs were reacted with aminefunctionalized, dye-doped mesoporous SiO2 spheres. The pores of the nanocomposite
could be further loaded with the anti-cancer drug doxorubicin and thus served as a
multimodal platform for optical imaging, MR contrast enhancement, and drug
delivery.
Fig. 5(b): Mesoporous SiO2 particles decorated with multiple Fe3O4 NPs [9]
CHAPTER VI
APPLICATIONS OF MAGNETIC NANOCOMPOSITES
6.1 MNC for high temperature applications
6.1.1 Transformers
Miniaturization and efficiency requirements demand the reduction of size and mass of core
materials in transformer. Increasing the Ms and will allow less magnetic material to be used
for a given transformer application. Decreasing Hc will reduce loss in AC applications,
improving efficiency. Operating temperatures may increase as power electronic systems
become more densely populated with components. This creates a need for magnetic materials
Department of Mechanical EngineeringPage 20
with increased operating temperatures. This can be achieved with nanocrystalline materials
with high crystalline and amorphous Tc to prevent particle decoupling.
6.1.2 DC-DC power converters
DC-DC power converters offer the advantage of reduced size and weight over conventional
line frequency transformer based power supplies. These converters are high frequency
devices that use magnetic transformers and inductors, along with active circuit elements, to
convert voltage levels. Ferrite materials are presently used to meet the frequency
requirements. The low Ms and Tc of ferrite materials limits the miniaturization potential of
converters. A magnetic material that had the Ms of iron and an operating frequency of 1 MHz
could result in a factor of 50 reduction in weight and volume. Nanocomposite magnetic
materials already have this Ms and have operating frequencies of 100 kHz. New, more
resistive nanocomposite structures have been conceived that will increase the operating
frequency above 1 MHz.
6.2 MNC for Biomedical Applications
6.2.1 Bio-imaging Probes
Fluorescence microscopy and nuclear MRI are two main imaging
techniques which have had a tremendous impact upon biomedical science
in recent years. Unlike previous approaches which may have required the
processing of fixed tissue samples, these techniques allow for the imaging
of live and intact organisms both in vivo and in vitro, resulting in a more
realistic picture of the processes occurring in live biological species.
Frequently, these imaging techniques are complimentary to each other
and could be used for parallel detection to have a clearer picture and
provide a correct diagnosis. In this case, fluorescent-magnetic
nanocomposites serve as new dual function contrast agents, which can be
used simultaneously in confocal fluorescent microscopy and in MRI. In
addition, fluorescent-magnetic nanocomposites allow us to perform optical
tracking of biological entities and processes in combination with
magnetophoretic manipulation.
There are several reports on the utilisation of multi-functional fluorescentmagnetic nanocomposites as contrast agents. These multi-functional
Department of Mechanical EngineeringPage 21
novel adsorbents which have large capacity of metal ions adsorption. Both
material design and adsorption kinetics have been systematically
investigated. Hierarchically structured metal oxides have two or more
levels of structure, which provide a high specific surface area, a high
surface-to-bulk
ratio, and surface functional groups that can interact with, e.g., heavy
metal ions for higher adsorption capacitance of 5.3 mg/g for As(III) and 5.4
mg/g for Cr(VI). The combination of iron minerals and carbon materials
shows an enhanced removal performance than each individual
component. For example, magnetite/ graphene oxide composite was
synthesized via a chemical reaction with a magnetite particle size of 10
15 nm, and was developed for the removal of cobalt(II) ions from aqueous
solutions with a maximum capacity of 22.70 mg/g at 343 K [11]. Other
materials, for example, polymer encapsuled magnetic NPs , iron oxide
coated sand , and Fe(II)Fe(III) hydroxysalt green rusts show great
potential to be used as promising adsorbents. In following section, two
typical adsorbents, carbon coated magnetic NPs and magnetic NPs
decorated graphene nanocomposites have been systematically studied for
Cr(VI) removal from waste water.
CHAPTER VII
CONCLUSION
The field of Magnetic nanocomposites is indeed very vast and still growing at a very fast
pace. It has great advantages and applications as discussed in the previous chapters. As it is
small in size it has great advantages like higher surface area which can carry drugs to the
biological systems. Also because of the smallness in the size of the particles it can be
transported to various parts of the body and can be detected by advanced technological
systems.
On the other hand, synthesis of high-quality magnetic nanoparticles in a controlled manner,
and detailed understanding of the synthetic mechanisms are still challenges to be faced in the
coming years. Synthesis of oxide or metallic magnetic nanoparticles often require the use of
toxic and/or expensive precursors, and the reaction is often performed in an organic phase at
high temperature at high dilution. These conditions to be maintained is a great challenge in
itself and the safety aspect of humans involved is to be considered.
One of the biggest challenges in biomedical applications of magnetic nanoparticles lies in
dealing with the issue of technology transfer. There are opportunities in this respect for more
interdisciplinary approaches, for example, to ensure that the laboratory based experiments
can more explicitly emulate the expected conditions that would be encountered in real life
situations. There is also scope for signicant contributions via the mathematical modelling of
complex systems, with the objective of understanding more specically the full gamut of
physical phenomena and effects that together determine whether, in the nal analysis, a given
application will be successful.
Magnetic nanocomposites offer to open new vistas in the area of drug delivery and they
promise as a prudent tactic to overcome the drug delivery related problems when the
problems of toxicity, localization and cost are addressed. If once the safety and hazardous
aspects of the materials is clearly understood and overcome, this field will certainly offer
much more benefits to mankind than it has already done.
CHAPTER VIII
REFERENCES
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