Selective N-monomethylation of aniline over Zn1-xNixFe2O4 (x=0, 0.2, 0.5, 0.8 and 1) type systems

The reaction of aniline with methanol was carried out over Zn1-xNixFe2O4 (x= 0, 0.2, 0.5, 0.8 and 1) type systems in a fixed-bed down-flow reactor. It was observed that systems possessing low ``x'' values are highly selective and active for mono N-alkylation of aniline leading to N-methyl aniline. Selectivity for N-methyl aniline over ZnFe2O4 was more than 99% under the optimized reaction conditions. Even at methanol to aniline molar ratio of 2, the yield of N-methyl aniline was nearly 55.5%, whereas its yield exceeded 67% at the molar ratio of 7. The Lewis acid sites of the catalysts are mainly responsible for the good catalytic performance. Cation distribution in the spinel lattice influences their acido-basic properties, and hence, these factors have been considered as helpful to evaluate the activity and stability of the systems.

Selective N-monomethylation of aniline using Zn1-x CoxFe2O4( x=0, 0.2, 0.5, 0.8 and 1.0)type systems

A series of ferrites having the general formula Zn1-xCoxFe2O4 (x=0, 0.2, 0.5, 0.8 and 1.0)were prepared by soft chemical route. The materials were characterized by adopting various physico-chemical methods. The reaction of aniline with methanol was studied in a fixed-bed reactor system as a potential source for the production of various methyl anilines. It was observed that systems possessing low ‘ x’ values are highly selective and active for N-monoalkylation of aniline leading to N-methylaniline. Reaction parameters were properly varied to optimize the reaction conditions for obtaining N-methylaniline selectively and in better yield. Among the systems Zn0.8Co0.2Fe2O4 is remarkable due to its very high activity and excellent stability. Under the optimized conditions N-methylaniline selectivity exceeded 98%. Even at a methanol to aniline molar ratio of 2, the yield of N-methylaniline was nearly 50%, whereas its yield exceeded 71% at the molar ratio of 5. ZnFe2O4, though executed better conversion than Zn0.8Co0.2Fe2O4 in the initial period of the run, deactivates quickly as the reaction proceeds. The Lewis acidity of the catalysts is mainly responsible for the good performance. Cation distribution in the spinel lattice influences their acido-basic properties and, hence, these factors have been considered as helpful parameters to evaluate the activity of the systems.

Selective alkylation of aniline to N-methyl aniline using chromium manganese ferrospinels

Various compositions of chromium manganese ferrospinels were tested as catalysts for the vapour phase alkylation of aniline with methanol. The samples were prepared by room temperature co-precipitation technique and characterized by various physico-chemical methods. The acidity–basicity determination revealed that the samples possess greater amount of basic sites than acidic sites. All the ferrite samples proved to be selective and active for N-monoalkylation of aniline leading to N-methyl aniline; Cr0.6Mn0.4Fe2O4, Cr0.8Mn0.2Fe2O4 and CrFe2O4 exhibited cent percent selectivity for N-methyl aniline. Neither C-alkylated products nor any other side products were detected for all catalyst samples. The catalytic activity of the samples studied in this reaction is related to their acid–base properties and also on the cation distribution. Under the optimized reaction conditions all the systems showed constant activity for a long duration.

Surface properties and catalytic activity of ferrospinels of nickel, cobalt and copper, prepared by soft chemical methods

Ferrospinels of nickel, cobalt and copper and their sulphated analogues were prepared by the room temperature coprecipitation route to yield samples with high surface areas. The intrinsic acidity among the ferrites was found to decrease in the order: cobalt> nickel> copper. Sulphation caused an increase in the number of weak and medium strong acid sites, whereas the strong acid sites were left unaffected. Electron donor studies revealed that copper ferrite has both the highest proportion of strong sites and the lowest proportion of weak basic sites. All the ferrite samples proved to be good catalysts for the benzoy lation of toluene with benzoyl chloride. copper and cobalt ferrites being much more active than nickel ferrite. The catalytic activity for benzoylation was not much influenced by sulphation, but it increased remarkably with calcination temperature of the catalyst. Surface Lewis acid sites, provided by the octahedral cations on the spinel surface, are suggested to be responsible for the catalytic activity for the benzoylation reaction.

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.

Lithium Containing Complex Metal Oxides and Metal phosphates:Investigations on their synthesis and various characterizations for rechargeable lithium battery applications

The work presented in the thesis is centered around two important types of cathode materials, the spinel structured LixMn204 (x =0.8to1.2) and the phospho -oIivine structured LiMP04 (M=Fe and Ni). The spinel system LixMn204, especially LiMn204 corresponding to x= 1 has been extensively investigated to understand its structural electrical and electrochemical properties and to analyse its suitability as a cathode material in rechargeable lithium batteries. However there is no reported work on the thermal and optical properties of this important cathode material. Thermal diffusivity is an important parameter as far as the operation of a rechargeable battery is concerned. In LixMn204, the electronic structure and phenomenon of Jahn-Teller distortion have already been established theoretically and experimentally. Part of the present work is an attempt to use the non-destructive technique (NDT) of photoacoustic spectroscopy to investigate the nature of the various electronic transitions and to unravel the mechanisms leading to the phenomenon of J.T distortion in LixMn204.The phospho-olivines LiMP04 (M=Fe, Ni, Mn, Co etc) are the newly identified, prospective cathode materials offering extremely high stability, quite high theoretical specific capacity, very good cycIability and long life. Inspite of all these advantages, most of the phospho - olivines especially LiFeP04 and LiNiP04 show poor electronic conductivity compared to LixMn204, leading to low rate capacity and energy density. In the present work attempts have been made to improve the electronic conductivity of LiFeP04 and LiNiP04 by adding different weight percentage MWNT .It is expected that the addition of MWNT will enhance the electronic conductivity of LiFeP04 and LiNiP04 with out causing any significant structural distortions, which is important in the working of the lithium ion battery.

Catalysis By Ferrites And Cobaltites For The Alkylation And Oxidation Of Organic Compounds

Catalysis is a very important process from an industrial point of view since the production of most industrially important chemicals involves catalysis.Solid acid catalysts are appealing since the nature of acid sites is known and their chemical behavior in acid catalyzed reactions can be rationalized by means of existing theories and models. Mixed oxides crystallizing in spinel structure are of special interest because the spinel lattice imparts extra stability to the catalyst under various reaction conditions so that theses systems have sustained activities for longer periods. The thesis entitled" Catalysis By Ferrites And Cobaltites For The Alkylation And Oxidation Of Organic Compounds " presents the preparation ,characterization ,and activity studies of the prepared spinels were modified by incorporating other ions and by changing the stoichiometry.The prepared spinels exhibiting better catalytic activity towards the studied reactions with good product selectivity.Acid-base properties and cation distribution of the spinels were found to control the catalytic activity.

Finite size effects on the structural and magnetic properties of sol–gel synthesized NiFe2O4 powders

Nanoparticles of nickel ferrite have been synthesized by the sol–gel method and the effect of grain size on its structural and magnetic properties have been studied in detail. X-ray diffraction (XRD) studies revealed that all the samples are single phasic possessing the inverse spinel structure. Grain size of the sol–gel synthesized powders has been determined from the XRD data and the strain graph. A grain size of 9 nm was observed for the as prepared powders of NiFe2O4 obtained through the sol–gel method. It was also observed that strain was induced during the firing process. Magnetization measurements have been carried out on all the samples prepared in the present series. It was found that the specific magnetization of the nanosized NiFe2O4 powders was lower than that of the corresponding coarse-grained counterparts and decreased with a decrease in grain size. The coercivity of the sol–gel synthesized NiFe2O4 nanoparticles attained a maximum value when the grain size was 15nm and then decreased as the grain size was increased further.

On the magnetic properties of ultra-Þne zinc ferrites

Zinc ferrite belongs to the class of normal spinels where it is assumed to have a cation distribution of Zn2`(Fe3`)2(O2~)4, and it is purported to be showing zero net magnetisation. However, there have been recent reports suggesting that zinc ferrite exhibits anomaly in its magnetisation. Zinc ferrite samples have been prepared by two di¤erent routes and have been analysed using low energy ion scattering, Mo¬ ssbauer spectroscopy and magnetic measurements. The results indicate that zinc occupies octahedral sites, contrary to the earlier belief that zinc occupies only the tetrahedral sites in a normal spinel. The amount of zinc on the B site increases with decrease in particle size. The LEIS results together with the Mo¬ ssbauer results and the magnetic measurements lead to the conclusion that zinc occupies the B site and the magnetisation exhibited by ultraÞne particles of zinc is due to short range ordering

Synthesis and Characterization of Magnetic Nanoparticles with High Magnetization and Good Oxidation Resistibility

Magnetic nanoparticles attract increasing attention because of their current and potential biomedical applications, such as, magnetically targeted and controlled drug delivery, magnetic hyperthermia and magnetic extraction. Increased magnetization can lead to improved performance in targeting and retention in drug delivery and a higher efficiency in biomaterials extraction. We reported an approach to synthesize iron contained magnetic nanoparticles with high magnetization and good oxidation resistibility by pyrolysis of iron pentacarbonyl (Fe(CO)[subscript 5]) in methane (CH[subscript 4]). Using the high reactivity of Fe nanoparticles, decomposition of CH[subscript 4] on the Fe nanoparticles leads to the formation of nanocrystalline iron carbides at a temperature below 260°C. Structural investigation indicated that the as-synthesized nanoparticles contained crystalline bcc Fe, iron carbides and spinel iron oxide. The Mössbauer and DSC results testified that the as-synthesized nanoparticle contained three crystalline iron carbide phases, which converted to Fe[subscript 3]C after a heat treatment. Surface analysis suggested that the as-synthesized and subsequently heated iron-iron carbide particles were coated by iron oxide, which originated from oxidization of surface Fe atoms. The heat-treated nanoparticles exhibited a magnetization of 160 emu/g, which is two times of that of currently used spinel iron oxide nanoparticles. After heating in an acidic solution with a pH value of 5 at 60°C for 20 h, the nanoparticles retained 90 percentage of the magnetization.

Optimizing the methods of synthesis for barium hexagonal ferrite: an experimental and theoretical study

M-type barium hexaferrite (BaM) is a hard ferrite, crystallizing in space group P6(3)/mmc possessing a hexagonal magneto-plumbite structure, which consists of alternate hexagonal and spinel blocks. The structure of BaM is thus related to those of garnet and spinel ferrite. However the material has proved difficult to synthesize. By taking into account the presence of the spinel block in barium hexagonal ferrite, highly efficient new synthetic methods were devised with routes significantly different from existing ones. These successful variations in synthetic methods have been derived by taking into account a detailed investigation of the structural features of barium hexagonal ferrite and the least change principle whereby configuration changes are kept to a minimum. Thus considering the relevant mechanisms has helped to improve the synthesis efficiencies for both hydrothermal and co-precipitation methods by choosing conditions that invoke the formation of the cubic block or the less stable Fe3O4. The role played by BaFe2O4 in the synthesis is also discussed. The distribution of iron from reactants or intermediates among different sites was also successfully explained. The proposed mechanisms are based on the principle that the cubic block must be self-assembled to form the final product. Thus, it is believed that these formulated mechanisms should be helpful in designing experiments to obtain a deeper understanding of the synthesis process and to investigate the substitution of magnetic ions with doping ions.

Ion dependence of magnetic anisotropy in MFe(2)O(4) (M = Fe, Co, Mn) nanoparticles synthesized by high-temperature reaction

The influence of different M(2+) cations on the effective magnetic anisotropy of systems composed of MFe(2)O(4) (M Fe, Co and Mn) nanoparticles was investigated. Samples were prepared by the high-temperature (538 K) solution phase reaction of Fe (acac) 3, Co (acac) 2 and Mn (acac) 2 with 1,2 octanodiol in the presence of oleic acid and oleylamine. The final particles are coated by an organic layer of oleic acid that prevents agglomeration. Transmission electron microscopy (TEM) images show that particles present near spherical form and a narrow grain size distribution, with mean diameters in the range of 4.5 - 7.6 nm. Powder samples were analyzed by ac susceptibility and Mossbauer measurements, and K(eff) for all samples was evaluated using both techniques, showing a strong dependence on the nature of the divalent cation. (C) 2008 Elsevier B.V. All rights reserved.

Surface spin disorder in nickel ferrite nanomagnets studied by in-field Mossbauer spectroscopy

The magnetic structure of NiFe(2)O(4) nanoparticles has been investigated by means of Mossbauer spectra at T=4.2 K in applied fields up to 12 T. Four samples were studied, with mean particle diameters ranging from 4.3 to 8.9 nm. All spectra could be decomposed into three sextets, two corresponding to the ferrimagnetic sublattices of Fe ions in the spinel structure (core) and the third one to randomly frozen spins near the particle surface (shell). The shell thickness, calculated from the fraction of disordered spins, was found to be about one-third of the particle radius at H (app)=e0 and to decrease with the applied field toward a common limit of similar to 0.4 nm. The mean canting angle relative to the field was also found to decrease for increasing fields, at a rate inversely correlated to the particle size.

Magnetic hysteresis loop shift in NiFe(2)O(4) nanocrystalline powder with large grain boundary fraction

Magnetic properties of nanocrystalline NiFe(2)O(4) spinel mechanically processed for 350 h have been studied using temperature dependent from both zero-field and in-field (57)Fe Mossbauer spectrometry and magnetization measurements. The hyperfine structure allows us to distinguish two main magnetic contributions: one attributed to the crystalline grain core, which has magnetic properties similar to the NiFe(2)O(4) spinel-like structure (n-NiFe(2)O(4)) and the other one due to the disordered grain boundary region, which presents topological and chemical disorder features(d-NiFe(2)O(4)). Mossbauer spectrometry determines a large fraction for the d-NiFe(2)O(4) region(62% of total area) and also suggests a speromagnet-like structure for it. Under applied magnetic field, the n-NiFe(2)O(4) spins are canted with angle dependent on the applied field magnitude. Mossbauer data also show that even under 120 kOe no magnetic saturation is observed for the two magnetic phases. In addition, the hysteresis loops, recorded for scan field of 50 kOe, are shifted in both field and magnetization axes, for temperatures below about 50 K. The hysteresis loop shifts may be due to two main contributions: the exchange bias field at the d-NiFe(2)O(4)/n-NiFe(2)O(4) interfaces and the minor loop effect caused by a high magnetic anisotropy of the d-NiFe(2)O(4) phase. It has also been shown that the spin configuration of the spin-glass like phase is modified by the consecutive field cycles, consequently the n-NiFe(2)O(4)/d-NiFe(2)O(4) magnetic interaction is also affected in this process. (C) 2010 Elsevier B.V. All rights reserved.

Structural and magnetic properties of chromium-doped ferrite nanopowders

This paper reports on a study of Cr(3+)-doped nanosized Ni-Zn ferrites produced by combustion reaction, and evaluates their morphological and magnetic properties. The powders were characterized by X-ray diffraction (XRD) and SEM and magnetic properties. All the compositions showed the formation of the inverse spinel phase of Ni-Zn ferrite. The average crystallite size ranged from 21 to 26 nm. The saturation magnetization was found to be in the range of 53-43 emu/g. The increase in Cr(3+) concentration in the Ni-Zn ferrite caused a reduction in hysteresis losses and a slight reduction in the saturation magnetization. (C) 2008 Elsevier B.V. All rights reserved.