Introduction to Ferrite Nanoparticles
Nanoparticles are those particles that are less than 100 nm in size . Nanotechnology is considered to be one of the most important future technologies involving several discipline of science including; solid state physics, solid state chemistry, materials engineering, medical science and biotechnology.
The transition from bulk to nanoscale leads to a number of changes in structural, physical, magnetic and electrical properties. Due to high DC electrical resistivity and low dielectric losses, nanoparticles are potential candidates as high frequency electromagnetic wave absorbers. High transition temperature (ferrimagnetic to paramagnetic) makes them ideal for high temperature applications.
Ferrite nano materials are chosen due to their high (>106 -cm) DC electrical resistivity, good magnetic properties, chemically stable over wide temperature range and low eddy current losses. They have potential applications in: Electromagnetic absorbers Data storage Microwave devices Core Material Drug delivery
The knowledge of cations distribution and spin alignment is essential to understand the magnetic and electrical properties of spinel ferrites. The DC electrical resistivity of ferrites can vary at room temperature from 10-2 -cm to 1011 -cm.
. Ferrites are iron containing complex oxide with interesting magnetic and electrical properties and have been studied extensively because of their important in basic as well as in applied research.
. Garnets (Me3Fe5O12) In spinel structure. cations rest on two types of interstitial sites to preserve the charge neutrality namely tetrahedral and octahedral sites.Ferrites can be classified into three different types Spinel ferrites (MFe2O4) Hexagonal ferrites (MFe12O19).
There are 64 tetrahedral sites in a spinel structure.
Fig. the fourth atom sits in the symmetrical position on top as shown in Fig. In a tetrahedral site the interstitial atom is in the center of a tetrahedral arrangement of four oxygen atoms at the lattice positions.
. 1. are in plane. Tetrahedral sites in unit cell. touching each other. 1. Three of them. Out of which 1/8 are occupied by the cations.
There are 32 octahedral sites in a spinel structure. Octahedral sites in unit cell. the other two are in asymmetrical position just above or below as shown in Fig.
. Four regular atoms are positioned in a plane. Out of which 1/2 are occupied by the cations. An octahedral position for an interstitial atom is the space in the interstices between 6 regular oxygen atoms at the face-centered positions forming an octahedral arrangement. 2. 2.
3+)A[De1. The spinel ferrites have been further classified into three categories due to the distribution of cations on tetrahedral (A-sites) and octahedral (B-sites) Types of spinel ferrites Normal spinel ferrites o [(De2+)A[D3+]BO4] Ferrimagnetic spinel Inverse spinel ferrites o [(D3+)A[De2+D3+]BO4 ] Intermediate spinel ferrites o [ (De 2+ D1.2+ D1+ 3+]BO4]
Classification of magnetic materials
Diamagnetism Paramagnetism Ferromagnetism Antferromagnetsim Ferrimagnetism
. mercury. Examples. diamagnetic material produces a weak magnetization that opposes the applied field giving rise to a negative susceptibility. So there are no net magnetic moments.Diamagnetism
The diamagnetic materials do not have any unpaired electrons. Gold. Copper. In response to an external applied fields.
Each atom possesses a permanent magnetic moment. so M=o
. all the magnetic moment randomly oriented. When H=0.
When magnetic field is applied the magnetic moments tend to orient themselves in the direction of the field. Zr
. Al. Cr. This result net magnetization and positive susceptibility Example.
Materials that retain a magnetization in zero field Magnetic moment are parallel alignment in the absence of an external magnetic field Examples: iron. cobalt
Thermal energy can be used to overcome exchange interactions Curie temp is a measure of exchange interaction strength
. exchange interactions favour antiparallel alignment of atomic magnetic moments Materials are magnetically ordered but have zero remnant magnetization and very low Many metal oxides are antiferromagnetic MnO CoO.Antiferromagnetism
In some materials.
f. Curie temp)
Thermal energy can be used to overcome exchange interactions Magnetic order is broken down at the Néel temperature (c.
Antiferromagnetic exchange interactions Different sized moments on each sublattice Results in net magnetization Example: magnetite. maghemite
The small region within which single direction of orientation of magnetic moment. Each domain is magnetized in a different direction
Ferromagnetic materials tend to form magnetic domains Domain.
Applying a field changes domain structure Domains with magnetization in direction of field grow Other domains shrink
Applying very strong fields can saturate magnetization by creating single domain
Removing the field does not necessarily return domain structure to original state Hence results in magnetic hysteresis
Magnetic susceptibility is sometimes written as And sometimes as the slope of M vs H
How does M respond to H?
There is a variety of ways that M responds to H Response depends on type of material Response depends on temperature Response can sometimes depend on the previous history of magnetic field strengths and directions applied to the material
Generally. the response of M to H is non-linear Only at small values of H or high temperatures is response sometimes linear M tends to saturate at high fields and low temperatures
low field magnetic susceptibility is inversely proportional to temperature Curie¶s Law
.Low field magnetic susceptibility
For some materials.
based upon the principle of mutual inductance.A high temperature AC magnetic susceptometer probe was fabricated. The instruments used for the construction of this apparatus include. 4: Block diagram representing the high temperature AC magnetic susceptibility measuring apparatus
Pick-up coils (primary and secondary) Heating element DC power supply (up to 30 Amp) A thick glass tube (8 mm) An exhaust fan A DC adapter (12 V) Pt-100 temperature sensor (up to 800 0C) Lock-in amplifier Multi-meters A wooden stand
Fig. That has an excellent agreement with the reported value 631±2 K [Charles Kittle] for pure Ni. 5. which was newly developed and to make it more and more precise.
The transition temperature for pure Ni measurement is found to be 633 ± 5 K. It was mandatory to calibrate the apparatus. Variation of inverse AC magnetic susceptibility with temperature for pure Ni.
Ferromagnetic material normally does not possesses net magnetization. At certain magnetic field.
. For external magnetic field. magnetic domains grows in size thus the material get a net magnetization. magnetization reaches a max value.
M depends on previous state of magnetization Remnant magnetization Mr remains when applied field is removed Need to apply a field (coercive field) in opposite direction to reduce M to zero.
Remnant magnetization is reduced to zero above Curie temperature Tc
.Effect of temperature on remnant magnetization
Heating a magnetized material generally decreases its magnetization.
Effect of temperature on remnant magnetization
Heating a sample above its Curie temperature is a way of demagnetizing it Thermal demagnetization
Wet Chemical Methods
co-precipitation Method Sol-Gel Method Microemulsion Method Hydrothermal Method
State reaction Method 2.
Solid State reaction Method Disadvantages
High temperature (>1100 0C) and long sintering times for reaction to complete o Slow reaction rate o Low homogeneity o Larger particle sizes (>100 nm)
Low sintering temperatures are required Short sintering time High degree of homogeneous (mixing at atomic level) High reaction rate Smaller particle size (<100 nm)
The method does not work well when: When the reactants have different solubility in water The reactants don¶t precipitate at the same rate
Co-precipitation consists of two processes: nucleation (formation of centers of crystallization) and a subsequent growth of particles. less dispersed in size and more chemically homogeneous. the mixing of reagents must be performed as fast as possible.
.In order to use co-precipitation as the synthesis route the following factors must be consider :
Rate of Mixing of Reagents:
The rate of mixing of reagents plays a vital role in the size of the resultant particles. To obtain ferrite particles of a smaller size. Less dispersed in size colloid is formed when the rate of nucleation is high and the rate of particles growth is low.
Influence of Temperature:
An increase in temperature in the range 20-1000C significantly accelerates formation of ferrite particles. This allows to obtain non-viscous primary suspension of particles that is important for better mixing of the reacting volume. and it is difficult to provide an intensive stirring. Influence of Concentration of Reagents:
Concentration of 0.
.1 to 0. At higher concentration (Me>0.2 mol/ is usually taken for the synthesis of ferrite particles. The activation energy for the formation of ferrites of different metals is not equal. .4mol/ ) suspension becomes viscous.
8 to 8. The most interesting fact is that a further increase of pH up to 12. Activation energy calculated from kinetics of the formation reaction for three different ferrites in the temperature range of 20-1000C decreases in the following sequence EA(Ni-ferrite) > EA(Co-ferrite) > EA(Zn-ferrite). -14 leads to a significant growth of the yield.
. the yield of ferrite grows when the pH of the reaction is increased from 6. Influence of pH of the Reaction: For the formation of ferrite. At high pH values the time of formation of ferrites become very short.6 followed by a slight increase. This sequence is also inagreement with the decreasing of dehydration temperature of the individual hydroxides of the corresponding metals.
we heated the precipitates for 30 min. In our case. The precipitates formed in a state which is easily filtered
.Duration of Heating after Co-precipitation: Co-precipitation takes place in a concentrated system. which may occur in such a system during long heating process. but no information is given on growing of particles size.
Then this product is subjected to heating in the precipitation alkaline solution to provide the transformation of metal hydroxides solution to the Co-Ni ferrites.
.xNi(OH)2. 6H2O + 2Fe(NO2)3 . At first solid hydroxides of metals in the form of colloidal particles are obtained by the co-precipitation of metal cations in alkaline medium.2Fe(OH)3 +2NaCl+6NaNO3 Co(1-x)NixFe2O4.nH2O + (4-n)H2O where n is an integer.
(1-x)Co(OH)2.9H2O +8NaOH (1-x)Co(OH)2. 6H2O + xNiCl2 . For the case of Co-Ni ferrites this reaction is : (1-x)CoCl2.