Cobalt (II), Nickel (II), and Copper (II) Complexes of Polystyrene-Supported Schiff Bases

Two novel polystyrene-supported Schiff bases, PSOPD and PSHQAD, were synthesized. A polymerbound aldehyde was condensed with o-phenylenediamine to prepare the Schiff base PSOPD, and a polymer-bound amine was condensed with 3-hydroxyquinoxaline-2-carboxaldehyde to prepare the Schiff base PSHQAD. This article addresses the study of cobalt (II), nickel (II), and copper (II) complexes of these polymer-bound Schiff bases. All the complexes were characterized, and the probable geometry was suggested using elemental analysis, diffuse reflectance ultraviolet, Fourier transform infrared spectroscopy, thermal studies, surface area studies, and magnetic measurements.

Studies on the preparation of Supported nickel catalysts using bis(ethylenediamine)nickel(II) complexes as precursors

Dept.of Applied Chemistry,Cochin University of Science and Technology

Surface Properties and Catalytic Activity of Ferrospinels Containing Cobalt, Nickel and Copper

The present study describes the surface properties and catalytic activities of ferrospinels containing Co, Ni and Cu prepared by the low temperature route. Various physico-chemical methods have been adopted to characterise the systems. The reactions carried out are the Friedel-Crafts benzoylation of aromatics and the cyclohexanol decomposition. We have attempted the sulphate modification of the ferrites and have studied the surface and catalytic properties of the sulphated analogues.The work is presented in six chapters, the last chapter giving the summary and conclusions of the results presented earlier. Our samples prove as potential catalysts for the benzoylation of aromatics , for which truly heterogeneous catalysts are rare. Again , the materials show remarkable dehydration/dehydrogenation activities during cyclohexanol decomposition. There is plenty of scope for research in this field, especially in the development of environmentally benign catalysts for acylation reactions.

Preparation and Characterization of Magnetic and Non-magnetic Nanosized Spinel Oxides, Nickel Nanoparticles and Nickel-Polymer Nanocomposites

Department of Physics, Cochin University of Science and Technology

Investigations on The Finite Size Effects of Some Inverse Spinels and Studies on Their Composites Based on Nitrile Rubber

Magnetism and magnetic materials have been an ever-attractive subject area for engineers and scientists alike because of its versatility in finding applications in useful devices. They find applications in a host of devices ranging from rudimentary devices like loud speakers to sophisticated gadgets like waveguides and Magnetic Random Access Memories (MRAM).The one and only material in the realm of magnetism that has been at the centre stage of applications is ferrites and in that spinel ferrites received the lions share as far as practical applications are concerned.It has been the endeavour of scientists and engineers to remove obsolescence and improve upon the existing so as to save energy and integrate in to various other systems. This has been the hallmark of material scientists and this has led to new materials and new technologies.In the field of ferrites too there has been considerable interest to devise new materials based on iron oxides and other compounds. This means synthesising ultra fine particles and tuning its properties to device new materials. There are various preparation techniques ranging from top- down to bottom-up approaches. This includes synthesising at molecular level, self assembling,gas based condensation. Iow temperature eo-precipitation, solgel process and high energy ball milling. Among these methods sol-gel process allows good control of the properties of ceramic materials. The advantage of this method includes processing at low temperature. mixing at the molecular level and fabrication of novel materials for various devices.Composites are materials. which combine the good qualities of one or more components. They can be prepared in situ or by mechanical means by the incorporation of fine particles in appropriate matrixes. The size of the magnetic powders as well as the nature of matrix affect the processability and other physical properties of the final product. These plastic/rubber magnets can in turn be useful for various applications in different devices. In applications involving ferrites at high frequencies, it is essential that the material possesses an appropriate dielectric permittivity and suitable magnetic permeability. This can be achieved by synthesizing rubber ferrite composites (RFC's). RFCs are very useful materials for microwave absorptions. Hence the synthesis of ferrites in the nanoregirne.investigations on their size effects on the structural, magnetic, and electrical properties and the incorporation of these ferrites into polymer matrixes assume significance.In the present study, nano particles of NiFe204, Li(!5Fe2S04 and Col-e-O, are prepared by sol gel method. By appropriate heat treatments, particles of different grain sizes are obtained. The structural, magnetic and electrical measurements are evaluated as a function of grain size and temperature. NiFel04 prepared in the ultrafine regime are then incorporated in nitrile rubber matrix. The incorporation was carried out according to a specific recipe and for various loadings of magnetic fillers. The cure characteristics, magnetic properties, electrical properties and mechanical properties of these elastomer blends are carried out. The electrical permittivity of all the rubber samples in the X - band are also conducted.

Evaluation of Magnetic,Dielectric and Mechanical Properties of Rubber Ferrite Composites

In the present study the preparation and characterisation of rubber ferrite composites (RFC) containing barium ferrite (BaF) and strontium ferrite (SrF) have been dealt with. The incorporation of the hard ferrites into natural and nitrile rubber was carried out according to a specific recipe for various loadings of magnetic fillers. For this, the ferrite materials namely barium ferrite and strontium ferrite having the general formula MO6Fe2O3 have been prepared by the conventional ceramic techniques. After characterisation they were incorporated into the natural and nitrile rubber matrix by mechanical method. Carbon black was also incorporated at different loading into the rubber ferrite composites to study its effect on various properties. The cure characteristics, mechanical, dielectric and magnetic properties of these composites were evaluated. The ac electrical conductivity of both the ceramic ferrites and rubber ferrite composites were also calculated using a simple relation. The investigations revealed that the rubber ferrite composites with the required dielectric and magnetic properties can be obtained by the incorporation of ferrite fillers into the rubber matrix, without compromising much on the processability and mechanical properties.

On the Synthesis and Multifunctional Properties of some Nanocrystalline Spinel Ferrites and Magnetic Nanocomposites

This thesis lays importance in the preparation and characterization of a few selected representatives of the ferrite family in the nanoregime. The candidates being manganese zinc ferrite and cobalt ferrite prepared by coprecipitation and sol-gel combustion techniques respectively. The thesis not only stresses importance on the preparation techniques and optimization of the reaction conditions, but emphasizes in investigating the various properties namely structural, magnetic and electrical. Passivated nickel nanocomposites are synthesized using polystyrene beads and adopting a novel route of ion exchange reduction. The structural and magnetic properties of these magnetic nanocomposites are correlated. The magnetocaloric effect (MCE) exhibited by these materials are also investigated with a view to finding out the potential of these materials as magnetic refrigerants. Calculations using numerical methods are employed to evaluate the entropy change on selected samples.

Template assisted fabrication of I-D nanostructures of Nickel,Cobalt, Iron Oxide and Carbon nanotubes and a study on their structural, magnetic and nonlinear optical properties for applications

Department of Physics, Cochin University of Science & Technology

Effect of mechanical milling on the structural, magnetic and dielectric properties of coprecipitated ultrafine zinc ferrite

Nanosized ZnFe2O4 particles containing traces of a-Fe2O3 by intent were produced by low temperature chemical coprecipitation methods. These particles were subjected to high-energy ball milling. These were then characterised using X-ray diffraction, magnetisation and dielectric studies. The effect of milling on zinc ferrite particles have been studied with a view to ascertaining the anomalous behaviour of these materials in the nanoregime. X-ray diffraction and magnetisation studies carried out show that these particles are associated with strains and it is the surface effects that contribute to the magnetisation. Hematite percentage, probably due to decomposition of zinc ferrite, increases with milling. Dielectric behaviour of these particles is due to interfacial polarisation as proposed by Koops. Also the defects caused by the milling produce traps in the surface layer contributes to dielectric permittivity via spin polarised electron tunnelling between grains. The ionic mechanism is enhanced in dielectrics with the rise in temperature which results in the increase of dielectric permittivity with temperature.

Studies on the structural, electrical and magnetic properties of composites based on spinel ferrites

This thesis mainly deals with the preparation and studies on magnetic composites based on spinel ferrites prepared both chemically and mechanically. Rubber ferrite composites (RFC) are chosen because of their mouldability and flexibility and the ease with which the dielectric and magnetic properties can be manipulated to make them as useful devices. Natural rubber is chosen as the Matrix because of its local availability and possible value addition. Moreover, NR represents a typical unsaturated nonpolar matrix. The work can be thought of as two parts. Part l concentrates on the preparation and characterization of nanocomposites based on y-Fe203. Part 2 deals with the preparation and characterization of RFCs containing Nickel zinc ferrit In the present study magnetic nanocomposites have been prepared by ionexchange method and the preparation conditions have been optimized. The insitu incorporation of the magnetic component is carried out chemically. This method is selected as it is the easiest and simplest method for preparation of nanocomposite. Nanocomposite samples thus prepared were studied using VSM, Mossbauer spectroscopy, Iron content estimation, and ESR spectroscopy. For the preparation of RFCs, the filler material namely nickel zinc ferrite having the general formula Ni)_xZnxFez04, where x varies from 0 to 1 in steps of 0.2 have been prepared by the conventional ceramic techniques. The system of Nil_xZn"Fe204 is chosen because of their excellent high frequency characteristics. After characterization they are incorporated into the polymer matrix of natural rubber by mechanical method. The incorporation is done according to a specific recipe and for various Loadings of magnetic fillers and also for all compositions. The cure characteristics, magnetic properties and dielectric properties of these composites are evaluated. The ac electrical conductivity of both ceramic nickel zinc ferrites and rubber ferrite composites are also calculated using a simple relation. The results are correlated.

Evidence for polaron conduction in nanostructured manganese ferrite

Nanoparticles of manganese ferrite were prepared by the chemical co-precipitation technique. The dielectric parameters, namely, real and imaginary dielectric permittivity (ε and ε ), ac conductivity (σac) and dielectric loss tangent (tan δ), were measured in the frequency range of 100 kHz–8MHz at different temperatures. The variations of dielectric dispersion (ε ) and dielectric absorption (ε ) with frequency and temperature were also investigated. The variation of dielectric permittivity with frequency and temperature followed the Maxwell–Wagner model based on interfacial polarization in consonance with Koops phenomenological theory. The dielectric loss tangent and hence ε exhibited a relaxation at certain frequencies and at relatively higher temperatures. The dispersion of dielectric permittivity and broadening of the dielectric absorption suggest the possibility of a distribution of relaxation time and the existence of multiple equilibrium states in manganese ferrite. The activation energy estimated from the dielectric relaxation is found to be high and is characteristic of polaron conduction in the nanosized manganese ferrite. The ac conductivity followed a power law dependence σac = Bωn typical of charge transport assisted by a hopping or tunnelling process. The observed minimum in the temperature dependence of the frequency exponent n strongly suggests that tunnelling of the large polarons is the dominant transport process

Evaluation of a.c. conductivity of rubber ferrite composites from dielectric measurements

The effect of frequency, composition and temperature on the a.c. electrical conductivity were studied for the ceramic, Ni1–xZnxFe2O4, as well as the filler (Ni1–xZnxFe2O4) incorporated rubber ferrite composites (RFCs). Ni1–xZnxFe2O4 (where x varies from 0 to 1 in steps of 0×2) were prepared by usual ceramic techniques. They were then incorporated into a butyl rubber matrix according to a specific recipe. The a.c. electrical conductivity (sa.c.) calculations were carried out by using the data available from dielectric measurements and by employing a simple relationship. The a.c. conductivity values were found to be of the order of 10–3 S/m. Analysis of the results shows that sa.c. increases with increase of frequency and the change is same for both ceramic Ni1–xZnxFe2O4 and RFCs. sa.c. increases initially with the increase of zinc content and then decreases with increase of zinc. Same behaviour is observed for RFCs too. The dependence of sa.c. on the volume fraction of the magnetic filler was also studied and it was found that the a.c. conductivity of RFCs increases with increase of volume fraction of the magnetic filler. Temperature dependence of conductivity was studied for both ceramic and rubber ferrite composites. Conductivity shows a linear dependence with temperature in the case of ceramic samples

Tailoring magnetic and dielectric properties of rubber ferrite composites containing mixed ferrites

Rubber ferrite composites containing various mixed ferrites were prepared for different compositions and various loadings. The magnetic and dielectric properties of the fillers as well as the ferrite filled matrixes were evaluated separately. The results are correlated. Simple equations are proposed to predetermine the magnetic and dielectric properties. The validity of these equations is verified and they are found to be in good agreement. These equations are useful in tailoring the magnetic and dielectric properties of these composites with predetermined properties

Inverse magnetocaloric effect in sol–gel derived nanosized cobalt ferrite

The magnetocaloric properties of cobalt ferrite nanoparticles were investigated to evaluate the potential of these materials as magnetic refrigerants. Nanosized cobalt ferrites were synthesized by the method of sol–gel combustion. The nanoparticles were found to be spherical with an average crystallite size of 14 nm. The magnetic entropy change ( Sm) calculated indirectly from magnetization isotherms in the temperature region 170–320 K was found to be negative, signifying an inverse magnetocaloric effect in the nanoparticles. The magnitudes of the Sm values were found to be larger when compared to the reported values in the literature for the corresponding ferrite materials in the nanoregime.

Effect of Carbon Black on the Mechanical and Dielectric Properties of Rubber Ferrite Composites Containing Barium Ferrite

Fine particles of barium ferrite (BaFe12O19) were synthesized by the conventional ceramic technique. These materials were then characterized by the X-ray diffraction method and incorporated in the natural rubber matrix according to a specific receipe for various loadings of ferrite. The rubber ferrite composites (RFC) thus obtained have several applications, and have the advantage of molding into complex shapes. For applications such as microwave absorbers, these composites should have an appropriate dielectric strength with the required mechanical and magnetic properties. The N330 (HAF) carbon black has been added to these RFCs for various loadings to modify the dielectric and mechanical properties. In this article we report the effect of carbon black on the mechanical and dielectric properties of these RFCs. Both the mechanical and dielectric properties can be enhanced by the addition of an appropriate amount of carbon black