Investigations on the Structural, Spectral and Magnetic Interactions of Transition Metal Complexes of Multidentate Ligands from Di-2-pyridyl ketone and N(4)-substituted Thiosemicarbazides

The present work deals with the investigations on sthe structural spectral and magnetic interactions of transition metal complexes of multidentate ligands from D1-2-pyridyl ketone and N(4)-Substituted thiosemicarbazides.Thiosemicarbazones are thiourea derivatives with the general formula R2N— C(S)—NH—N=CR2. In the solution state, the thiosemicarbazones exhibit the thionethiol tautomerism similar to the keto-enol tautomerism, and in solution state the thiol form predominates and a deprotonation at the thiolate group in alcoholic medium enhances the coordination abilities ofthe thiosemicarbazones.The magnetochemistry of metal complexes of di-2-pyridyl ketone is a current hot subject of research, which mainly owes to the excellent structural diversity of the complexes ranging from cubanes to clusters, with promising ferromagnetic outputs.Only few efforts were aimed at the magnetochemistry of metal complexes of thiosemicarbazones, and that too were concerned with the complexes of bisttltioscinicarbazones). However, as far as the monothiosemicarbazones are concerned, the magnetochemistry of transition metal complexes of di-2-pyridyl ketone thiosemicarbazones turned up quite unexplored. Consequently, an investigation into it appeared novel and promising to us and that prompted this study, which can be regarded as the initial step towards exploring the magnetochemistry of thiosemicarbazone complexes, especially of di-2-pyridyl ketone derivatives.We could successfully isolate single crystals suitable for X-ray diffraction for the first three ligands. To conclude, we have synthesized some new thiosemicarbazones and their transition metal complexes and studied their structural, spectral and magnetic attributes. Some ofthe complexes revealed interesting stereochemistries and possible bridging characteristics with spectroscopic evidences. Unfortunately, single crystal Xray diffraction studies could not be carried out for many of these interesting compounds due to the lack of availability of suitable quality single crystals. However, the magnetic studies provided support for the proposed stereochemistry giving evidences for their magnetically concentrated nature. The magnetic susceptibilities measured at six different temperatures in the 80-298 K range are fitted into different magnetic equations, which provided an idea about the magnetic behavior of the compounds under study. Some of the copper, oxovanadium, nickel and cobalt complexes are found to possess anomalous magnetic moments, i.e., they revealed no regular gradation with temperature. However, some other copper complexes are observed to be antiferromagnetic, due to super-exchange pathways. The manganese complexes and one of the cobalt complexes are also observed to be antiferromagnetic in nature. However, some nickel complexes have turned up to be ferromagnetic. Accordingly, the versatile stereoehemistry and magnetic behavior of the complexes studied, prompt us to conclude that the transition metal complexes of di-2-pyridyl ketone thiosemicarbazones are promising systems for potential magnetic applications.

Annealing inducedlowcoercivity,nanocrystallineCo–Fe–Si thin films exhibitinginversecosine angular variation

Co–Fe–Si based films exhibit high magnetic moments and are highly sought after for applications like soft under layer sinper pendicular recording mediatomagneto-electro-mechanical sensor applications.In this workt he effect of annealing on s tructural,morphologicaland magnetic propertiesofco–Fe–Si thin films wasinvestigated.compositional analysis using x-rayphotoelectron spectroscopy and secondary ion massspectroscopyrevealedanativeoxidesurfacelayerconsistingofoxidesofco,feandsionthe surface. The morphology of theas deposited films shows mound like structures conformingtothe Volmer–Webergrowthmodel.Nanocrystallisationofamorphous films upon annealing was observed by glancing anglex-raydiffraction and transmission electron microscopy.Theevolutionofmagnetic properties with annealing is explained using the Herzermodel.Vibrating sample magnetometry measurements carried out at various angles from01 to 901 to the applied magnetic field were employed to study the angula rvariation of coercivity.The angular variation fits the modified Kondorsky model. Interestingly,the coercivity evolution with annealing deduced frommagneto-opticalKerreffectstudies indicates areversetrendcomparedtomagetisationobservedinthebulk.Thiscanbeattributedtoa domain wallpinningatnativeoxidelayeronthesurfaceofthin films. Theevolutionofsurfacemagnetic properties iscorrelatedwithmorphologyevolutionprobedusingatomicforcemicroscopy.The morphology aswellasthepresenceofthenativeoxidelayerdictatesthesurfacemagneticproperties and this is corroborated by the apparent difference in the bulk and surface magnetic properties

Manifestation of Colossal Thermoelectric Power by Charge Ordered Small and Intermediate Bandwidth Manganites

Thermoelectric materials are revisited for various applications including power generation. The direct conversion of temperature differences into electric voltage and vice versa is known as thermoelectric effect. Possible applications of thermoelectric materials are in eco-friendly refrigeration, electric power generation from waste heat, infrared sensors, temperature controlled-seats and portable picnic coolers. Thermoelectric materials are also extensively researched upon as an alternative to compression based refrigeration. This utilizes the principle of Peltier cooling. The performance characteristic of a thermoelectric material, termed as figure of merit (ZT) is a function of several transport coefficients such as electrical conductivity (σ), thermal conductivity (κ) and Seebeck coefficient of the material (S). ZT is expressed asκσTZTS2=, where T is the temperature in degree absolute. A large value of Seebeck coefficient, high electrical conductivity and low thermal conductivity are necessary to realize a high performance thermoelectric material. The best known thermoelectric materials are phonon-glass electron – crystal (PGEC) system where the phonons are scattered within the unit cell by the rattling structure and electrons are scattered less as in crystals to obtain a high electrical conductivity. A survey of literature reveals that correlated semiconductors and Kondo insulators containing rare earth or transition metal ions are found to be potential thermoelectric materials. The structural magnetic and charge transport properties in manganese oxides having the general formula of RE1−xAExMnO3 (RE = rare earth, AE= Ca, Sr, Ba) are solely determined by the mixed valence (3+/4+) state of Mn ions. In strongly correlated electron systems, magnetism and charge transport properties are strongly correlated. Within the area of strongly correlated electron systems the study of manganese oxides, widely known as manganites exhibit unique magneto electric transport properties, is an active area of research.Strongly correlated systems like perovskite manganites, characterized by their narrow localized band and hoping conduction, were found to be good candidates for thermoelectric applications. Manganites represent a highly correlated electron system and exhibit a variety of phenomena such as charge, orbital and magnetic ordering, colossal magneto resistance and Jahn-Teller effect. The strong inter-dependence between the magnetic order parameters and the transport coefficients in manganites has generated much research interest in the thermoelectric properties of manganites. Here, large thermal motion or rattling of rare earth atoms with localized magnetic moments is believed to be responsible for low thermal conductivity of these compounds. The 4f levels in these compounds, lying near the Fermi energy, create large density of states at the Fermi level and hence they are likely to exhibit a fairly large value of Seebeck coefficient.

Studies on Magnetic Iron Oxide Loaded Activated Carbon

The current water treatment technology is oriented towards the removal of contaminants, mostly organic compounds, by activated carbon. Activated carbons are classified as Granular Activated Carbons (GAC) and Powdered Activated Carbons (PAC) on the basis of the particle size of the carbon granules. Powdered carbons are generally less expensive than granular carbon, operating costs with powdered carbon could be lower. Though powdered activated carbon has many advantages over granular carbon, its application in large-scale separation process is limited by difficulty in recovery and regeneration. Deposition of magnetic iron oxide on carbon particles provides a convenient way of recovering the spent carbon from process water. The study deals with the preparation and physico-chemical characterization of magnetic iron oxide loaded activated carbons. The evaluation of absorption properties of magnetic iron oxide loaded activated carbon composites. The target molecules studied were phenol, p-nitro phenol and methylene blue. The feasibility of magnetic separation of iron oxide loaded activated carbons were studied and described in this thesis.

Studies on the Effect of High Energy Ball Milling On the Structural, Electrical and Magnetic Properties of Some Normal Spinets in the Ultrafine Regime

The present work is an attempt to understand the characteristics of high energy ball milling on the structural, electrical and magnetic properties of some normal spinets in the ultra fine regime, Magnetism and magnetic materials have been a fascinating subject for the mankind ever since the discovery of lodestone. Since then, man has been applying this principle of magnetism to build devices for various applications. Magnetism can be classified broadly into five categories. They are diamagnetic, paramagnetic, ferromagnetic antiferromagnetic and ferrimagnetic. Of these, ferro and ferri magnetic materials assume great commercial importance due to their unique properties like appropriate magnetic characteristics, high resistivity and low eddy current losses. The emergence of nanoscience and nanotechnology during the last decade had its impact in the field of magnetism and magnetic materials too. Now, it is common knowledge that materials synthesized in the nanoregime exhibit novel and superlative properties with respect to their coarser sized counterparts in the micron regime. These studies reveal that dielectric properties can be varied appreciably by high-energy ball milling in nanosized zinc ferrites produced by coprecipitation method. A semi conducting behaviour was observed in these materials with the Oxygen vacancies acting as the main charge carrier for conduction, which was produced at the time of coprecipitation and milling. Thus through this study, it was possible to successfully investigate the finite size effects on the structural, electrical and magnetic properties of normal spinels in the ultra fine regime

Fabrication of thin films and nano columnar structures of Fe-Ni amorphous alloys and modification of its surface properties by thermal annealing and swift heavy ion irradiation for tailoring the magnetic properties

Department of Physics, Cochin University of Science and Technology

Acid-base, electron-donating and magnetic properties of Nd2O3 and its mixed oxides with alumina catalysts

The electron donor properties of Nd2O3 activated at 300, 500 and 800°C were investigated through studies on the adsorption of electron acceptors of various electron affinities - 7, 7, 8,8-tetracyanoquinodimethane (2.84 eV). 2, 3, 5, 6-tetrachloro-l , 4-benzoquinone (2.40 eV). p-dinitrobenzene (1.77 eV), and m-dinitrobenzene (1.26 eV) in solvents acetonitrile and 1, 4-dioxan. The extent of electron transfer during adsorption has been found from magnetic measurements and electronic spectral data. The corresponding data on mixed oxides of neodymium and aluminium are reported for various. compositions. The acid-base properties of catalysts were also determined using a set of Hammett indicators.

Electron-donating, acid-base, and magnetic properties of samaria catalyst

The electron-donor properties of Sm2O3 activated at 300, 500, and 800°C are reported from studies on the adsorption of electron acceptors of various electron affinities (electron affinity values in eV are given in parentheses): 7,7,8,8-tetracyanoquino-dimethane (2.84), 2,3,5,6-tetrachloro-1,4-benzoquinone (2.40), p-dinitrobenzene (1.77), and m-dinitrobenzene (1.26) in acetonitrile and 1,4-dioxane. The extent of electron transfer during the adsorption was determined from magnetic measurements. The acid-base properties of Sm2O3 at different activation temperatures are reported using a set of Hammett indicators. Electron donor-acceptor interactions at interfaces are important in elucidating the adhesion forces.

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

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.

A simple linear magnetic field sweep generator for magnetic resonance experiments

A simple and inexpensive linear magnetic field sweep generating system suitable for magnetic resonance experiments is described. The circuit, utilising a modified IC bootstrap configuration, generates field sweep over a wide range of sweep durations with excellent sweep linearity.

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

Magnetic field-induced cluster formation and variation of magneto-optical signals in zinc-substituted ferrofluids

Fine magnetic particles (size≅100 Å) belonging to the series ZnxFe1−xFe2O4 were synthesized by cold co-precipitation methods and their structural properties were evaluated using X-ray diffraction. Magnetization studies have been carried out using vibrating sample magnetometry (VSM) showing near-zero loss loop characteristics. Ferrofluids were then prepared employing these fine magnetic powders using oleic acid as surfactant and kerosene as carrier liquid by modifying the usually reported synthesis technique in order to induce anisotropy and enhance the magneto-optical signals. Liquid thin films of these fluids were prepared and field-induced laser transmission through these films was studied. The transmitted light intensity decreases at the centre with applied magnetic field in a linear fashion when subjected to low magnetic fields and saturate at higher fields. This is in accordance with the saturation in cluster formation. The pattern exhibited by these films in the presence of different magnetic fields was observed with the help of a CCD camera and was recorded photographically.