The crystallographic and magnetic properties of manganese oxides belonging to the Ruddlesden Popper (RP) series, described by the formula A_n+1B_nO_3n+1, are presented. Compounds having n = 2, 3 and ∞ are discussed in Chapters 3, 4 and 5, respectively, their properties being studied by powder X-ray and neutron diffraction, SQUID magnetometry and magnetotransport measurements. In Chapter 3 (A₃B₂O₇) it is shown that Sr_2-xNd_1+xMn₂O₇ (0 ≤ x ≤ 0.5) and Sr₂PrMn₂O₇ exhibit colossal, negative magnetoresistance (CMR) below 150K. The zero field resistivity signal is reduced by 2-3 orders of magnitude in a field of 14T, at ~4.2K. The compounds Sr₂HoMn₂O₇ and Sr₂YMn₂O₇ show no significant magnetoresistance. In contrast to the tetragonal Sr,Nd and Sr,Pr compositions, these compounds show a symmetry lowering to space group P4₂/mnm, and spin glass freezing on the Mn sublattice at ~20K. Chapter 4 (A₄B₃O₁₀) focuses on A- and B-cation substitutions in the parent compound Ca₄Mn₃O_10-δ. Substitution of Ca by Sr yields Sr₄Mn₃O_10-δ, an orthorhombic (Cmca) compound, composed of trimers of face sharing octahedra. The magnetic susceptibility of this sample is interpreted in terms of direct and indirect antiferromagnetic (AFM) Mn-Mn exchange interactions. The orthorhombic (Pbca) RP phase Ca_3.95La_0.05Mn₃O_10-δ has a magnetic transition at ~114K, suggesting that the antiferromagnetic groundstate, with associated weak ferromagnetism arising through the Dzyaloshinsky-Moriya interaction observed in Ca₄Mn₃O_10-δ, is preserved on introduction of a fraction of La³⁺ dopant cations. Ca_3.95La_0.05Mn₃O_10-δ displays CMR at 4K, with the resistivity signal reduced to 18% of the zero field value, in 14T. B-cation substitution yields Ca₄Mn₂TiO_9.93, an orthorhombic (Pbca) RP phase in which the Mn:Ti cation distribution, deduced from the combined results of anomalous dispersion X-ray experiments and neutron diffraction studies, is 59.8%(2.6):40.2%(2.6) and 70.1%(1.3):29.9%(1.3) across the 4b and 8c octahedral sites, respectively. Neutron diffraction studies at 5K show the presence of only short range magnetic interactions in this insulating material, the resistivity of which is reduced by just 10% at 75K in 14T. Chapter 5 (ABO₃ or A₂BB'O₆) describes the mixed B-cation phases, La₂GaMnO₆ and Nd₂GaMnO₆, containing Mn³⁺, 3d⁴ cations. Both are cation disordered, orthorhombic (Pnma) materials, and Nd₂GaMnO₆ exhibits a static, cooperative Jahn-Teller (JT) distortion. La₂GaMnO₆ contains a relatively higher proportion of dynamic, cooperative JT distortions, and as such exhibits isotropic ferromagnetism at 5OK and 5K (2.80(5)μ_B per Mn aligned along y at 5K), predicted by the 'quasistatic hypothesis', which describes the correlation between electron spin configurations of neighbouring JT cations. The magnetic structure of Nd₂GaMnO₆ at 5K and 1.7K is modelled as 'A_X F_Y G_Z' for the Mn sublattice, and 'F_γ' for the Nd sublattice, using Bertaut's notation, resulting in competing ferromagnetic and antiferromagnetic superexchange interactions on the Mn sublattice along the [010] direction of the unit cell. Both materials are highly insulating and neither displays CMR, with resistivity values in each being reduced to just 96% of the zero field value at 200K, in a field of 14T.

[Truncated abstract] In the past decade, the synthesis of superparamagnetic iron oxide nanoparticles (SPIONs) has received considerable attention due to their potential applications in biomedical fields. However, success in size and shape control of the SPIONs has been mostly achieved through organic routes using large quantities of toxic or/and expensive precursors in organic reaction medium at high reaction temperature. This has limited the biomedical applications of SPIONs and therefore, development of a synthetic method under aqueous condition that is reproducible, scalable, environmentally benign, and economically feasible for industrial production is of paramount importance in order to fully realise their practical applications. Spinning Disc Processing (SDP) has been used to synthesise superparamagnetic magnetite (Fe3O4) nanoparticles at room temperature via a modified chemical precipitation method under continuous flow condition and offer a potential alternative to be applied to SPIONs production. SDP has extremely rapid mixing under plug flow conditions, effective heat and mass transfer, allowing high throughput with low wastage solvent efficiency. The synthesis process involves passing ammonia gas over a thin aqueous film of Fe2+/3+ which is introduced through a jet feed close to the centre of a rapidly rotating disc (500-2500 rpm). Synthetic parameters such as precursor concentrations, temperature, flow rate, disc speed, and surface texture influence the particle sizes. ... Magnetic silica microspheres are receiving great attention for possible applications in magnetic targeting drug delivery, bioseparation and enzyme isolation. However, the current available methods for preparation suffer from the setback of low loading of Fe3O4 nanoparticles in the silica microsphere, which result in low magnetic moment, thereby limiting their practical applications. Therefore it is of considerable importance to develop new alternative synthetic methods for fabricating magnetic silica microspheres with high magnetic nanoparticles loading. Superparamagentic Fe3O4 nanoparticles (8-10 nm diameter) and curcumin have been encapsulated in mesoporous silica in a simple multiplestep self assembly approach process with high Fe3O4 nanoparticles loading (37%). The synthesis involves loading of curcumin in the Cetyltrimethylammonium bromide (CTAB) micellar rod in the presence of superparamagnetic Fe3O4 nanoparticles via a parallel synergistic approach. The synthesised magnetic mesoporous silica composite material is stable, superparamagnetic with high saturation magnetisation before and after curcumin leaching experiment. Under physiological pH in phosphate buffer, the curcumin is slowly released over several days. These magnetic mesoporous silica are expected to have great potential as targeted drug delivery systems.

Powder neutron diffraction and magnetic susceptibility measurements of the antiferromagnetic phases of Mn_xNi_1-xO,Mn_xCo_1-xO, (Mn_xFe_1-x)_zO and (Co_xFe_1-x)_zO reveal that the magnetic moments of unlike ions are always effectively collinear, despite the presence of competing anisotropies. The magnetic moments of Mn_xNi_1-xO (x = 0.24,0.48 and 0.77) at 5K are confined to (111) planes by dipole-dipole forces, and the small trigonal exchangestrictions are the products of opposed antiferromagnetic Mn²⁺-Mn²⁺ and ferromagnetic Ni²⁺-Mn²⁺ nearest neighbour interactions. In Mn_xCo_1-xO (x = 0.05, 0.10, 0.25,0.36) at 5K, the orbital degener- acy of Co²⁺ is removed by both Jahn-Teller (J.T) and spin-orbit coupling (S.O) mechanisms, leading to orthorhombic or triclinic symmetries and partially quenched Co²⁺ moments. Monoclinic symmetry is observed for 0.51<x<0.67, and Jahn-Teller stabilisations and spin-only Co²⁺ moments are evident. The cobalt concentration is too small to support a cooperative J.T stabilisation in Mn_0.83Co_0.17O, where a magnetostriction (c/a < 1) is observed (in agreement with previous AFMR results). Previous results for Co_xNi_1-xO, and those for Mn_xCo_1-xO, (Mn_xFe_1-x)_zO (x = 0.05, 0.1, 0.12, 0.23, 0.36,0.56,0.66,0.89) and (Co_xFe_1-x)_zO (x = 0.04,0.12,0.50,0.63,0.81) at 5K indicate that the anisotropy order for the iron group monoxides is CoO>MnO»Fe_zO≈NiO. The weak trigonal anisotropy of Fe²⁺ correlates with the near-cubic symmetries of (Co_xFe_1-x)_z( (x = 0.04,0.12) and (Mn_xFe_1-x)_zO (0.1<x<0.66), and a tetragonal (c/a>1) magnetostriction of Fe²⁺ is observed in (Co_xFe_1-x)_zO with x > 0.5. Measurements of vacancy-ferric interstitial ratios for (Mn_xFe_1-x)_zO and (Co_xFe_1-x)_zO suggest that non-stoichiometry is accommodated by 6:2 or 8:3 defect clusters in the former, and by larger units in the latter. The observed magnetic moments of defective samples are normally larger than those calculated according to a previous model for Fe_zO, and require the postulation of partial antiferromagnetic order around the clusters. The room temperature Mossbauer effect parameters of (Mn_xFe_1-x)_zO (0<x<0.975,0.910<z<1.0) indicate that while Fe²⁺ and Mn²⁺ ions are randomly distributed over octahedral sites, ferric ions are localised around defect clusters.

Thesis (Ph.D.)--Materials Science and Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Snyder, Robert; Committee Co-Chair: Wang, Zhong Lin; Committee Member: El-Sayed, Mostafa; Committee Member: Milam, Valeria; Committee Member: Summers, Christopher; Committee Member: Wong, C. P.

Thin films (5nm ± 2nm thick) of ZrO2, Al2O3, TiO2, Sm, Gd, Zr, Ni, and Pt were deposited onto TbFeCo films (100nm ± 20nm thick) on silicon and graphite substrates and analyzed with XPS as prospective candidates for TbFeCo diffusion barriers. Metals were chosen primarily according to electronegativity. Samples were typically heated to 272°C in UHV for 20 hours to enhance diffusion. Experiments with the metals were performed in a more consistent manner than with the oxides. The Sm, Gd, and Zr were reactively oxidized during the deposition. The Sm/Sm-oxide and Gd/Gd-oxide appeared to be favorable candidates for TbFeCo diffusion barriers. TbFeCo was not detected near the surface before or after heating the samples to 272°C for 20 hours and depth profiles indicated oxygen contamination decreased steadily as the barrier/TbFeCo interface was approached. For the other materials examined, either the oxides were reduced (at least partially) during heating to 272°C (381°C for Al₂O₃) or diffusion of TbFeCo was detected after heating, indicating that they would not be favorable candidates for TbFeCo diffusion barriers.

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Submitted in the fulfillment of the requirement for the Master's Degree in Chemistry,Durban University of Technology, 2017. / Knoevenagel condensation reaction is a useful protocol for the formation of C=C bond in organic synthesis. This protocol is extensively utilized by synthetic chemist to generate dynamic intermediates or end-products such as perfumes, polymers, pharmaceuticals and calcium antagonists. The reaction is catalyzed by bases such as ammonia, primary and secondary amines, quaternary ammonium salts, Lewis acids, catalysts containing acid-base sites, which are carried out under homogeneous conditions. This necessitates the use of organic solvent which generate the large volumes of solvent waste. From green chemistry perspective, solvent free heterogeneous catalysts have received considerable attention. Since, these heterogeneous catalysts not only avoid the use of organic solvents but also suppress side reactions such as self-condensation and oligomerisation leading in better selectivity and product yield. In recent years, therefore, the use of heterogeneous catalyst, their recovery and reusability are in demand in industry. The use of cobalt, iridium and platinum hydroxyapatites, MgO/ZrO2, MgO/HMCM- earlier been reported in the literature, and used as heterogeneous catalysts for the Knoevenagel condensation of aldehydes and esters. Based on these evidences, we envisioned that MgO and VMgO could also be used as heterogeneous catalysts for this reaction. Magnesium oxide was synthesized from three precursors, viz. magnesium nitrate, magnesium carbonate and magnesium acetate. Magnesium oxide prepared from magnesium nitrate precursor was found to be the optimum giving an 81 % product yield. Vanadium-magnesium oxide catalysts with different vanadium loadings; 1.5, 3.5 and 5.5 wt. %, were synthesized by wet impregnation of magnesium oxide with aqueous ammonium metavanadate solution. The synthesized catalysts were characterized by ICP-AES, FTIR, Powder XRD, SEM-EDX and TEM. The Knoevenagel condensation reactions between benzaldehyde and ethyl cyanoacetate were carried out in a 100 mL two-necked round bottom flask equipped with a reflux condenser, magnetic stirrer and a CaCl2 guard tube. An equimolar quantity (10 mmol) of substrates and 0.05g of catalyst were added to the flask and heated at 60 °C, stirred vigorously for the required time. The yields were determined using GC-FID equipped with a capillary column. Elemental composition of the catalysts (vanadium and MgO) was determined by ICP-AES. IR spectra of MgO showed that magnesium oxide was the only phase present in the catalysts prepared from different precursors. The 1.5 and 5.5 wt. % VMgO showed weak bands attributed to pyrovanadate and orthovanadate phases present in small quantities. The phases manifested more with the increase in the vanadium concentration (3.5 and 5.5 wt. % VMgO). The diffraction patterns of all the catalysts showed the existence of MgO and magnesium orthovanadate. The morphology of the catalysts with increasing vanadium was more affected by precursor treatment rather than chemical differences. Electron microscopy showed that the VMgO surface is only sparingly covered with vanadium and MgO showed stacked with large rounded particles. Good to excellent yields were obtained for the MgO catalysts: MgO(1) 68 %, MgO(2) 65 %, MgO(3) 72 %, MgO(P) 73 % and MgO(DP) 82 %. Excellent yields were obtained for the VMgO catalysts: 1.5VMgO 83 %, 3.5VMgO 91 % and 5.5VMgO 97 %. The 5.5VMgO catalyst was found to be the optimum catalyst and was further tested for it activity using different aldehyde substrates. Excellent yields of the products were obtained for benzaldehyde 97 %, nitrobenzaldehyde 94 %, bromobenzaldehyde 96 %, chlorobenzaldehyde 93 % and methoxybenzaldehyde 95%. / M

Studies to compare and elucidate some of the surface chemical characteristics of chromium dioxide and barium ferrite magnetic particles have been performed. These investigations primarily involved using the technique of flow microcalorimetry to look at the interaction of molecular probes (pyridine, 4-nitrophenol) and various components present in a magnetic ink (dispersants and model binder compounds) with the particles. The interactions were measured in terms of heats of adsorption and adsorption density. Ancillary experiments using FTIR and XPS were also performed. Both electrophoretic measurements and calorimetric studies showed that stabilized CrO₂ was less acidic than un-stabilized CrO₂. Similar measurements showed that un-doped barium ferrite was more acidic than Co and Ti doped barium ferrite. The interactions of dispersants and model binder components with barium ferrite were found to be very exothermic; heats of interaction of greater than -20 kcal/mole were not uncommon. Subsequent analysis of barium ferrite particles treated with dispersants and binder compounds using FTIR and XPS suggested that these compounds formed chemical complexes on the surface of the ferrite particles.

This work details the synthesis and growth mechanisms of 1D magnetic and semiconducting nanostructures. Specifically, magnetic iron oxide and ZnS-SiO2 nanowires are examined. These materials are chosen due to their promise for biomedical and electronic applications and the perceived need to both create these structures as tools for these applications and to understand their formation processes so that they can be manufactured at a scale and efficiency suitable for commercialization. The current state and impact of nanotechnology is discussed through the lens of continuing technological advances and environmental factors, and the term is defined according to a specific set of criterion involving size, utility, and uniqueness. Details of synthesis and characterization of Fe3O4, ε-Fe2O3, and ZnS-SiO2 core-shell nanowires are presented. Observations regarding the growth of these structures are paired with additional experiments, simple simulations, and other literature to discuss the classical VLS growth process in general, and its applicability to these structures in particular. Finally, some exciting future applications are discussed, with details for initial experimental work presented in the appendix.

High dielectric constant materials have tremendous impact on miniaturization of devices that are used in various applications like wireless communication systems, microelectronics, global positioning systems, etc. To store electric charge in a very small space necessarily needs a capacitor with very high dielectric constant. Thus, these materials are very important in fabricating capacitors, or metal oxide semiconductor filed effect transistor (MOSFET). Among the existing commercially available devices, silicon-based microelectronic devices are commonly used based on the moderately stable dielectric constants of silicon with low losses and minimal temperature and frequency dependence. However, now-a-days, the perovskite based transition metal oxides have drawn attention that have the ability to fulfill all the requirements for being a good dielectric material in all the industrial applications. In this thesis we have studied a few selected perovskite based transition metal oxide systems in terms of their dielectric and magnetic behaviour. In Chapter 1, we have have given brief introductions about the some application of dielectric materials and the origin of dielectric and magnetic properties in the materials. We have also discussed about the polarisation in the dielectric materials to understand it’s frequency dependence and also to formalise different relaxation behaviour with the help of physical and mathematical explanation. In Chapter 2, we describe the various methodologies adopted in this thesis. In Chapter 3, we have studied the dielectric behaviour of Nd2NiMnO6, a rare earth based double perovskite ferromagnetic insulator. We successfully synthesised and characterised the compounds, settled the valency issues with the help of temperature dependent XAS of the transition metal atom in contrast to the existing controversy available in literature. We have found that this material shows relaxor kind behaviour with a colossal dielectric constant value. We have studied in details the origin of the colossal dielectric constant and the relaxation behaviour along with the a.c and d.c. transport properties. We have shown the origin of the ferromagnetism (TC ∼ 200 K) with a low temperature antiferromagnetic ordering (TN ∼ 55 K) with the help of detailed studies of temperature dependent d.c., a.c. magnetism and their XMCD. We have also investigated the isothermal variation of magnetodielectric and magnetoresistance behaviour as a function of magnetic field and their origin. In Chapter 4,we study the effect of cation anti-site disorder on the magnetic, dielectric and transport properties of another rare earth based ferromagnetic double perovskite insulator La2NiMnO6 by controlling different extent of anti-site disordered. We have confirmed the valency of the transition metal cations using XAS technique and followed by shown, different types of magnetic interaction between the transition metal cations using d.c magnetic, quantitative XMCD analysis and the origin of large dielectric response, a.c. transport & dielectric relaxation using temperature variation dielectric measurement as an experimental evidence in contrast of our previous speculation published in literature. We further have studied, the coupling between the magnetic and electric spin through isothermal magnetodielectric measurement. In Chapter 5, we have successfully synthesised and characterised a solid solution of YMnxIn1−xO3 series via different mol % of In doping in the multiferroic YMnO3 system. YMnO3 is a well known multiferroic material studied rigorously during past few decades. We have seen, YMnO3 which has a antiferromagnetic ordering temperature of ∼ 75 K suppressed with increasing the dopant concentration In. We have figured out the effect of In doping in the suppression of multiferroic phase and extended it to the dielectric properties. We have found that, the temperature dependence of dielectric constant shows an anomaly at the magnetic ordering temperature and studied magnetodielectric coupling. We have also investigated the temperature variation of dielectric relaxation and a.c. transport behaviour as a function of composition. In Chapter 6, we have identified the phase seperation and proposed a phase diagram as function of Gd doping in the Ho2−xGdxCuTiO6 double perovskite, where two end member, namely Ho2CuTiO6 and Gd2CuTiO6 are found to be in two different crystallographic phase as, hexagonal (P63cm) and orthorhombic (Pnmm), respectively. We have characterised the valency of the transition metal cations using XAS.We have seen very less temperature and frequency dependence of dielectric constant in hexagonal phase in compare to the orthorhombic phase and tried to figuring out from experimental analysis by performing temperature dependence dielectric const measurement. We also have shown the effect of doping in the origin of dielectric relaxation, a.c transport and magnetic behaviour of this system. In Chapter 7, we have synthesised and characterised successfully two different rare earth based layered perovskite La3Cu2VO9 and La4Cu3MoO12 compounds are of centrosymmetric space group. We have figured it of the valency of the different atoms present in the compound using XAS. We also do have observed the good temperature stability of dielectric constant of these materials and explored origin of mechanism in the dielectric relaxation, a.c. transport property by performing the temperature dependance dielectric measurement. The magnetic structure also have shown with the help of d.d. magnetic measurements. In Appendix A, we have seen the very stable dielectric constant constant from very low to above room temperature of the 2D nano PbS. The frequency stability of dielectric constant is also remarkable in compare to bulk PbS values available in literature. We have explored the origin of the conductivity and relaxation mechanism performing dielectric constant measurement. In conclusion, we investigate, in this thesis, dielectric properties of different transition metal oxides system and the mechanism of dielectric relaxation, a.c, d.c transport and their origin of magnetic response.