EXPERIMENTAL TECHNIQUES

EXPERIMENTAL TECHNIQUE

Chapter I1

2.1 Composition Of Ferrites A series of mixed ferrites of various compositions were fabricated by ~ ' solid state reaction technique. The substitution of rare earth ions ( ~ d and ~ d ~ in )Ni,Fe~.~04and CuxNil.,Fe204 spinel system was studied respectively. ' were fabricated and studied in detail. The following compos~tions
1. Nio~Fe20 4 . N ~5Fe2 7 o

N ~,Fez 304 Nio 9Fe24 0 4 . o and

2. Cu,Nil.,Fe~04withx=0.2, 0.3,0.4,0.5, 0.6,0.7, 0.8and0.9.

2.2 Sample Preparation

These samples were prepared by solid state reaction, having general
0 chemical formula NixFe(3~x, 4 (where X = 0.3, 0.5, 0.7, 0.9) were prepared by

taking necessary amount of NiC12 and iron powder according to stioch~ornetrlc ratio NixFe,3.r, 0
4

2.3 Stiochiometric Calculation

The weight percentage of the chemicals to be mixed for various samples was calculated by using the formula. Number of moles =weight I molecular weight The required amount of each chemical was weighed using electronic balance having an accuracy of 1 0 ' ~gms. The calculated weights of the chemicals, molecular weights of the chemicals and wt % calculated for each sample were prepared. 2.4 Formation Of Samples The nickel chloride and iron powder of AR grade were weighed and dissolved in dilute nitric acid and then heated slowly to evaporate the solvent. The resulting black-brown precipitate was collected in a (remaining sample was transferred) porcelain crucible and was kept in a furnace.

Chapter /I
2.5 Heat Treatment

For the nickel ferrite the heat treatment was performed in the box furnace. The temperature of the furnace was increased from the room temperature to 5 0 0 ' ~for flve hours. Then it was allowed to cool slowly till it reached the room temperature. The fired sample was ground thoroughly. The fired sample was ground thoroughly and divided into three parts. To the two parts of the weighed samples, 5% by weight of gadolinium fluoride and neodymium fluoride were added respectively. It was kept in the furnace once again and heated to 850c for five hours. After cooling it was ground to a fine powder. The copper nickel ferrite was also prepared similarly 2.6 Fourier Transform lnfra Red Spectroscopy: FTlR spectroscopy is used pr~marilyfor qualitatwe and quantitative analys~s organic compounds and is also useful for determining the chemical of structure of many inorganic and biological compounds. The early-stage IR instrument is of the dispersive type, which uses a prism or a grating monochromator. The dispersive instrument is characteristic of a slow scanning. A Fourier Transform lnfrared (FTIR) spectrometer obtains infrared spectra by first collecting an interferogram of a sample signal with an Interferometer, whlch measures all of infrared frequencies simultaneously. An FTIR spectrometer acquires and digitizes the interferogram, performs the FT function, and outputs the spectrum.

2.6.1 Working Principle Of FTlR

The main component in (FTIR) spectrometer is an interferometer. lnfrared radiation can be analyzed by means of a scanning Michelson interferometer figure (2.1). Th~s consists of a moving mirror (4). a fixed mirror

(3),and a beam splitter (c). Radiation from the infrared source (0)is collimated

Chapter I1
by a mirror (2), and the resultant beam a divided at the beam splitter and, for any particular wavelength, constructively or destructively interfere, depending on the difference in optical paths between the two arms of the interferometer. With a constant mirror velocity, the intensity of the emerging radiation at any particular wavelength modulates in a regular sinusoidal manner. In the case of a broadband source the emerging beam is a complex mixture of modulation frequencies that, after passing through the sample compartment;
IS

focused

onto the detector (G). This detector signal is sampled at preclse intervals during the mirror scan. Both the sampling rate and the mirror velocity are controlled by a reference signal incident upon a detector (E), which is produced by modulation of the beam from the helium-neon laser (A). The resulting signal from detector (G) is known as an interferogram and contalns all the rnformatlon required to reconstruct the spectrum vla the mathematical process known as Fourier transformation. The computer can perform the Fourier transformat~on calculation and present an infrared spectrum, which plots absorbance (or transmittance) versus wavenumber. A KBr beam splitter coated with Ge is typically used for mid IR region and its resolution is 0.5cm.' and wave number ranges from 7800 to 100 cm-' Mid FTlR absorption spectra for all samples are obtained from the IR spectrometer. The instrument used in the present case is FTlR SHIMADZU 8700. 2.6.2 Interpreting The Spectrum lnfrared (IR) spectroscopy is a chemical analytical technique, which measures the infrared Intensity versus wavelength (wavenumber) of light. Based on the wavenumber, infrared light can be categorized as far infrared (4-400cm-'), mid infrared (400-4,000cm.') and near 1nfrared(4,000-4,000cm.'). lnfrared spectroscopy detects the vibration characteristics of chemical functional groups in a sample. When an infrared light interacts with the matter, chemical bonds will stretch, contract and bend. As a result, a chemical

Chapter 11
functional group tends to adsorb infrared radiation in a specific wavenumber range regardless of the structure of the rest of the molecule. The correlation of the band wavenumber position with the chemical structure is used to identify a functional group in a sample. The wavenumber positions where functional groups adsorb are consistent, despite the effect of temperature, pressure, sampling, or change in the molecule structure in other parts of the molecules. Thus the presence of specific functional groups can be mon~toredby these types of infrared bands, which are called group wavenumbers. The IR regions are classifled as follows: Near lR 12500 - 4000 cm wave no ) (0.8 - 2.5 I J ~wavelength. Mid IR

'

Far IR

200 - 12.5 cm-'

The graph produced shows percentage transm~ssion against wave number. If no radiation is absorbed at a particular frequency, then the l ~ n e on the graph will be at 100% at the corresponding wave number. Absorption due to different types of bonds occupies characteristic regions of the spectrum as shown in the figure(2.2). Most functional groups absorb above 1500 cm~'.The region below 1500 cm-' is known as the "fingerprint region". Every molecule produces a unique pattern here, so if an unknown sample produces a spectrum which matches that of a known compound, the sample can be confirmed to be that compound. The infrared region (4000-650cm-') is of great Importance in studying an organic and other compounds. Since infrared spectrum contain a large number of bands no two compound will have the same infrared spectrum (except optical

Chapter I1
isomers). Thus infrared spectrum may be regarded as the fingerprint of a molecule. The functional group region : 4000-1300cm~'(2.5-7.7lm) The finger print region: 1300-909cm-'(7.7-11.Oum) The higher frequency portion (1400-1300cm~')is called the functional group region. The characteristic stretching frequencies for important functional groups such as OH, NH, C=O etc occur in this portion of the spectrum. The absence of absorption in the assigned ranges for the various functional groups is an evidence for the absence of such groups in the molecule. It should be noted that certain structural characteristics may cause a band to become extremely broad so that it may go unnoticed. Overtones and combination tones of lower frequency bands frequently appear in the high frequency region of the spectrum. In general, the high frequency regions show absorption arising from stretching vibrations which are useful for the identification of functional group. Infact, the region from 1400-650cm.'
IS

called finger print region because

the pattern of absorption in this region is unique of a particular compound. This intermediate portion of the spectrum, especially the 130-909cm~'region, is usually complex since both stretching and bending modes give rise to absorption in this region. The absorption bands in the finger print reglon are also complex with the bands originating in interacting vibrational modes. Organlc, inorganic and other compounds have their own unique absorption in this region. This region contalns many absorption by bending vibrations and the region is particularly rich in absorption bands and shoulders. Although similar type of molecules may show similar spectra in the high frequency region 40001300cm~', there will always be a clear difference in the finger print region. The spectrum In the fingerprint region is very sensitive and pattern of the ~nfrared changes even with minor chemical or stereo chemical alteration in the molecule. The fingerprint region of the spectrum is extremely valuable when examined with reference to the other regions.

Based on intensity, the bands in an infrared spectrum are generally classified: strong(s), medium(m), weak(w) and variable(v). The position of all the bands are expressed in cm".

2.6.3 The Theory

In a molecule, the atoms are not held rig~dlyapart. Instead they can move, as if they are attached by a spring of equilibrium separation Re. This bond can either bend or stretch. If the atoms in a bond are subjected to infrared radiation of a specific frequency (between 300 - 4000cm"), they will absorb the energy, and the bond will move from the lowest vibrational state to the next higher. In a simple diatomic molecule, there is only one direction of vibration. stretching. This means there is only one band of infrared absorption. Weaker bonds require less energy, as if the bonds are springs of different strengths. If there are more atoms, there will be more bonds, and therefore more modes of vibrations. This will produce a more complicated spectrum. For a linear molecule with "n" atoms, there are 311-5 vibrational modes. If it is nonlinear, it will have 3n-6 modes. For example, water (HzO),has 3 atoms, and is non linear: therefore it has (3'3)-6 = 3 modes of vibration. There is one important restriction that the molecule will only absorb radiation if the vibration is accompanied by a change in the dipole moment of the molecule. A dipole occurs when there is a difference of charge across a bond. If the two oppositely charged molecules get closer or further apart as the change. Hooke's law is required to bond bends or stretches, the moment w~ll calculate the frequency of light absorbed.

Chapter 11
Where k =force constant indicating the strength of the bond, m, and m2 are the masses of the two atoms. By looklng at this equation, we can see that if there is a high value of k, i.e. the bond is strong, it absorbs higher frequency of light. So, a C=C double bond would absorb at higher frequency of light than a C-C single bond. Also, the larger the two masses, the lower the frequency of light absorbed.

2.7 X-Ray Diffraction Studies

X-ray diffraction is a standard structural characterization technique for bulk materials that has been successfully applled to nanostructures. The XRD pattern contains information on the composition and crystallographic phases of the material, average grain size, lattice strains, grain boundary characteristics, and, through its temperature and pressure dependence, on thermal properties. Quite a few reports provide a comprehensive and in-depth analysis of XRD spectra [X. Zhu et al. (1987). R. Milkove et al. (1985)l.In the present case K. a Panalylical X pert pro is used for the analysis. The typical p~cture the XRD of is as shown in the figure [2.3].

2.7.1 Powder Pattern And Structure

1. The d-spacing of lattice planes depends on the size of the elementary cell
and determines the position of the peaks.
2. The intensity of each peak is caused by the crystallographic structure, the

positlon of the atoms within the elementary cell and their thermal vibration.

3. The line width and shape of the peaks may be derived from conditions of
measuring and properties - l~ke particle size - of the sample material.

Chapter /I
2.8 Magnetic Studies
The study of magnetic properties of materials involves the understandingof electronic behaviour in condensed matter. Many varieties of inorganic compounds and alloys of transition metals have been synthesized wherein the electrons show highly correlated behaviour; i.e. the conduction electrons depend on the presence or absence of neighbouring electrons. These electronic correlations result in changes in magnetism, superconductivity, metal-insulator transitions or heavyfermion behaviour of conduction electrons. These d~fferenttypes of behaviour depend upon the strength of Coulomb and exchange interactions among electrons. The study of these interactions among electrons requires magnetic measurement at low temperatures and high magnet~cfields. Many types of magnetometers have been developed and are now commercially available. They have been extensively reviewed by Fonerl,2 and can be broadly classified into two categories: (i) Those employing direct techniques, such as measurement of the force experienced by the specimen In a non-uniform field (Guoy, Faraday, Kahn balances); (ii) Those based on indirect techniques such as measurement of magnetic Induction due to relative motion between the sample and the detection coils system (vibrating sample, vibrating coil. SQUIDS)or use of galvanomagnetic effects such as the Hall effect The vibrat~ngsample magnetometer (VSM) developed originally by Foner2 has, however, been the most successful for low temperature and high magnet~c field studies of correlated electron systems due to its simplicity, ruggedness, ease of measurement and reasonably high sensitivity.

2.8.1 Working Principle Of VSM A vibrating 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 and can tell us information about the changing magnetic field. A VSM is used to measure the magnetic behavior of magnetic materials. The sample to be studled is kept in a constant magnetic field.

Chaoter 11
If the sample IS magnetic, this constant magnetic field will magnetize the sample by alignlng the magnetic domains, or the individual magnetic spins, wtth the field. The stronger the constant field, the larger the magnetizationwill be. The magnetic dipole moment of the sample will create a magnetic field around the sample, somet~mes called the magnetic stray field. As the sample is moved up and down. this magnetic stray field is changing as a function of time and can be sensed by a set of pick-up coils. The alternating magnetic field w~ll cause an electric current in the pick-up coils according to Faraday's Law of Induction. This current will be proportional to the magnetization of the sample. The greater the magnetization, the greater the induced current. The induction current is amplified by a transimpedance amplifier and lock-in amplifier. The various components are hooked up to a computer interface. Using controlling and rnonitor~ng software, the system can tell us how much the sample is magnetized and how its magnetization depends on the strength of the constant magnetic field. A typical measurement of a sample is taken in Lake Shore 7404 in the following manner. The typical picture is shown in the figure( 2.4) i) The strength of the constant magnetic fleld is set. ii) The sample begins to vibrate iii) The signal received from the probe is translated into a value proporlional to for the magnetic moment of the sample iv) The strength of the constant magnetic field changes to a new value and no data is taken during thls transition v) The strength of the constant magnetic field reaches its new value vi) The signal from the probe again gets translated into a value for the magnetization of the sample. vii) The constant magnetic field varies over a given range, and a plot of

Chapter 11
magnetization (M) versus magnetic field strength (H) is generated. A schematic diagram of the VSM shown in the figure(2.5).

2.9 Electrical Studies

The AC electrical conductivity stud~esare carried out using Zentech 3305 Automatic Component Analyzer. The instrument is used to determine the conductance and capacitance of the sample. The 3305 Automat~ccomponent Analyzer is an automatic instrument which used for testing and analyzing in are components. The testing functions includ~ng this un~t : L, C, R, Z. Basic Accuracy : Basic 0.1% (1KHz 1 1V rms) Measurement Range L
-

0 . 0 0 1H ~

Measurement Frequency : 20Hz to 1MHz Measurement Voltage : 10mV to 2V rms, each step IOmV.

Fig(2.1) Schematic diagram of FTlR

Triple bond
S~ngle bond
sttetch

. Cloubln

Flngerpnnt t e g l o n

-.,....

. . .,

A. * .

..

I . .

. . . . ..
I

I . YLJ

4000

3000

2000

1500

1000

600

Wavenurnbe, (cm ')

Fig (2.3 ) The photograph of the Panalytical XRD

Fig (2.5) Schematic diagram of vibrating sample magnetometer