Novel Magnetic Materials Based on Macrocyclic Ligands: Towards High Relaxivity Contrast Agents and Mononuclear Single-Molecule Magnets

The preparation and characterization of coordination complexes of Schiff-base and crown ether macrocycles is presented, for application as contrast agents for magnetic resonance imaging, Project 1; and single-molecule magnets (SMMs), Projects 2 and 3. In Project 1, a family of eight Mn(II) and Gd(III) complexes of N3X2 (X = NH, O) and N3O3 Schiff-base macrocycles were synthesized, characterized, and evaluated as potential contrast agents for MRI. In vitro and in vivo (rodent) studies indicate that the studied complexes display efficient contrast behaviour, negligible toxicity, and rapid excretion. In Project 2, DyIII complexes of Schiff-base macrocycles were prepared with a view to developing a new family of mononuclear Ln-SMMs with pseudo-D5h geometries. Each complex displayed slow relaxation of magnetization, with magnetically-derived energy barriers in the range Ueff = 4 – 24 K. In Project 3, coordination complexes of selected later lanthanides with various crown ether ligands were synthesized. Two families of complexes were structurally and magnetically analyzed: ‘axial’ or sandwich-type complexes based on 12-crown-4 and 15-crown-5; and ‘equatorial’ complexes based on 18-crown-6. Magnetic data are supported by ab initio calculations and luminescence measurements. Significantly, the first mononuclear Ln-SMM prepared from a crown ether ligand is described.

Investigation of Frustrated Quasi-One-Dimensional Quantum Spin-Chain Materials

Copper arsenite CuAs2O4 and Copper antimonite CuSb2O4 are S=1/2 (Cu2+ 3d9 electronic configuration) quasi-one-dimensional quantum spin-chain compounds. Both compounds crystallize with tetragonal structures containing edge sharing CuO6 octahedra chains which experience Jahn-Teller distortions. The basal planes of the octahedra link together to form CuO2 ribbon-chains which harbor Cu2+ spin-chains. These compounds are magnetically frustrated with competing nearest-neighbour and next-nearest-neighbour intrachain spin-exchange interactions. Despite the similarities between CuAs2O4 and CuSb2O4, they exhibit very different magnetic properties. In this thesis work, the physical properties of CuAs2O4 and CuSb2O4 are investigated using a variety of experimental techniques which include x-ray diffraction, magnetic susceptibility measurements, heat capacity measurements, Raman spectroscopy, electron paramagnetic resonance, neutron diffraction, and dielectric capacitance measurements. CuAs2O4 exhibits dominant ferromagnetic nearest-neighbour and weaker antiferromagnetic next-nearest-neighbour intrachain spin-exchange interactions. The ratio of the intrachain interactions amounts to Jnn/Jnnn = -4.1. CuAs2O4 was found to order with a ferromagnetic groundstate below TC = 7.4 K. An extensive physical characterization of the magnetic and structural properties of CuAs2O4 was carried out. Under the effect of hydrostatic pressure, CuAs2O4 was found to undergo a structural phase transition at 9 GPa to a new spin-chain structure. The structural phase transition is accompanied by a severe alteration of the magnetic properties. The high-pressure phase exhibits dominant ferromagnetic next-nearest-neighbour spin-exchange interactions and weaker ferromagnetic nearest-neighbour interactions. The ratio of the intrachain interactions in the high-pressure phase was found to be Jnn/Jnnn = 0.3. Structural and magnetic characterizations under hydrostatic pressure are reported and a relationship between the structural and magnetic properties was established. CuSb2O4 orders antiferromagnetically below TN = 1.8 K with an incommensurate helicoidal magnetic structure. CuSb2O4 is characterized by ferromagnetic nearest-neighbour and antiferromagnetic next-nearest-neighbour spin-exchange interactions with Jnn/Jnnn = -1.8. A (H, T) magnetic phase diagram was constructed using low-temperature magnetization and heat capacity measurements. The resulting phase diagram contains multiple phases as a consequence of the strong intrachain magnetic frustration. Indications of ferroelectricity were observed in the incommensurate antiferromagnetic phase.

Structural, Magnetic and Thermal Studies of Ce1-xEuxCrO3 Nano-Powders

A new series of nano-sized Ce1-xEuxCrO3 (x = 0.0 to 1.0) with an average particle size of 50 - 80 nm were synthesized using a solution combustion method. Nano-powders Ce1-xEuxCrO3 with the canted antiferromagnetic property exhibited interesting magnetic behaviours including the reversal magnetization and the exchange bias effect. The effect of europium doping as the ion with the smaller radius size and different electron con figuration on structural, magnetic and thermal properties of Ce1-xEuxCrO3 were investigated using various experimental techniques, i.e. DC/AC magnetic susceptibility, heat capacity, thermal expansion, Raman scattering, X-ray photoemission spectroscopy, transmission/scanning electron microscopy, X-ray powder diffraction and neutron scattering. An exchange bias effect, magnetization irreversibility and AC susceptibility dispersion in these samples confirmed the existence of the spin disorder magnetic phase in Ce1-xEuxCrO3 compounds. The exchange bias phenomenon, which is assigned to the exchange coupling between glassy-like shell and canted antiferromagnetic core, showed the opposite sign in CeCrO3 and EuCrO3 at low temperatures, suggesting different exchange interactions at the interfaces in these compounds. The energy level excitation of samples were examined by an inelastic neutron scattering which was in good agreement with the heat capacity data. Neutron scattering analysis of EuCrO3 was challenging due to the large neutron absorption cross-section of europium. All diffraction patterns of Ce1-xEuxCrO3 showed the magnetic peak attributed to the antiferromagnetic Cr3+ spins while none of the diffraction patterns could detect the magnetic ordering of the rare-earth ions in these samples.

Caractérisation et modélisation de l’aimant organique NIT-2Py

L'aimant organique NIT-2Py a été caractérisé expérimentalement et ses propriétés ont été simulées numériquement à partir de la théorie de la fonctionnelle de la densité. Le magnétisme dans ce matériau provient de la présence d'un électron non apparié sur chaque molécule qui a ainsi un moment magnétique non nul. Ceci a été confirmé par des simulations sur une molécule isolée. Les molécules de NIT-2Py cristallisent dans le groupe d'espace P21/c avec huit molécules par maille élémentaire pour former la structure cristalline Alpha étudiée dans ce document. Le moment effectif de la susceptibilité et l'entropie magnétique totale montre que ce matériau est un système de spins 1/2 avec un spin par molécule. Les mesures de chaleur spécifique ont mis en évidence la présence de deux phases magnétiques ordonnées à basse température qui sont séparées par un plateau en aimantation. Une première phase est observée à des champs magnétiques inférieurs à 2.2 T et a une température de transition de 1.32 K en champ nul. Les mesures de susceptibilité magnétique et d'aimantation ont permis d'établir que cette phase ordonnée est antiferromagnétique. Ceci est confirmé par les simulations numériques. La deuxième phase est induite par le champ magnétique avec une température de transition de 0.53 K à 6 T. L'information disponible sur cette phase est limitée et l'étude du système à l'extérieur des phases ordonnées en donne une meilleure compréhension. Un modèle de spins S=1/2 isolés et de dimères S=0 isolés reproduit bien les mesures d'aimantation et de chaleur spécifique au-dessus de 3 K. L'application d'un champ magnétique réduit l'écart d'énergie entre le singulet et le triplet du dimère jusqu'au croisement qui se produit à 6 T. La phase induite émerge précisément à ce croisement et on spécule l'existence d'un condensat de Bose-Einstein des états triplets.

Preparation and Characterisation of Spinel Ferrites - Their Incorporation in Rubber Matrix and Evaluation of Properties

The objectives of the proposed work are preparation of ceramic nickel zinc ferrite belonging to the series Ni1-XZnXFe2O4 with x varying from 0 to 1in steps of 0.2, structrural, magnetic and electrical characterization of Ni1-XZnXFe2O4, preparation and evaluation of Cure characteristics of Rubber Ferrite Composites (RFCs), magnetic characterization of RFCs using vibrating sample magnetometer (VSM), electrical characterization of RFCs and estimation of magnetostriction constant form HL parameters. The study deals with the structural and magnetic properties of ceramic fillers, variation of coercivity with composition and the variation of magnetization for different filler loadings are compared and correlated. The dielectric properties of ceramic Ni1-XZnXFe2O4 and rubber ferrite composites containing Ni1-XZnXFe2O4 were evaluated and the ac electrical conductivity (ac) of ceramic as well as composite samples can be calculated by using a simple relationship of the form ac = 2f tan 0r, with the data available from dielectric measurements. The results suggest that the ac electrical conductivity is directly proportional to the frequency

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.

Impact of zinc substitution on the structural and magnetic properties of chemically derived nanosized manganese zinc mixed ferrites

Mn1-xZnxFe2O4 nanoparticles (x=0-1) were synthesized by wet chemical co-precipitation techniques. X-ray diffraction, transmission electron microscopy and high-resolution transmission electron microscopy were effectively utilized to investigate the different structural parameters. The elemental analysis was conducted using energy-dispersive spectrum and inductively coupled plasma analysis. The magnetic properties such as magnetization and coercivity were measured using vibrating sample magnetometer. The observed magnetization values of the nanoparticles were found to be lower compared to the bulk counterpart. The magnetization showed a gradual decrease with zinc substitution except for a small increase from x=0.2 to 0.3. The Curie temperature was found to be enhanced in the case of ferrites in the nanoregime. The variation in lattice constant, reduced magnetization values, variation of magnetization with zinc substitution, the presence of a net magnetic moment for the zinc ferrite and the enhancement in Curie temperature in Mn1-xZnxFe2O4 all provide evidence to the existence of a metastable cation distribution together with possible surface effects at the nanoregime.

Ferrofluid thin films as optical gaussmeters proposed for field and magnetic moment sensing

Ferrofluids belonging to the series, Ni x Fe1-x Fe2O4 and Zn x Fe1-x Fe2O4, were synthesized using cold co-precipitation. Liquid films of these ferrofluids were prepared by encapsulating the ferrofluids in between two optically smooth and ultrasonically cleaned glass plates. Magnetic field induced laser transmission through these ferrofluid films has been investigated. Magnetic field values can be calibrated in terms of output laser power in the low field region in which the variation is linear. This set up can be used as a cheap optical gaussmeter in the low field regime. Using the same set-up, the saturation magnetization of the sample used can also be calculated with a sample that is pre-characterized. Hence both magnetization of the sample, as well as applied magnetic field can be sensed and calculated with a precalibrated sample.

Synthesis of Bio-Compatible SPION–based Aqueous Ferrofluids and Evaluation of RadioFrequency Power Loss for Magnetic Hyperthermia

Bio-compatible magnetic fluids having high saturation magnetization find immense applications in various biomedical fields. Aqueous ferrofluids of superparamagnetic iron oxide nanoparticles with narrow size distribution, high shelf life and good stability is realized by controlled chemical co-precipitation process. The crystal structure is verified by X-ray diffraction technique. Particle sizes are evaluated by employing Transmission electron microscopy. Room temperature and low-temperature magnetic measurements were carried out with Superconducting Quantum Interference Device. The fluid exhibits good magnetic response even at very high dilution (6.28 mg/cc). This is an advantage for biomedical applications, since only a small amount of iron is to be metabolised by body organs. Magnetic field induced transmission measurements carried out at photon energy of diode laser (670 nm) exhibited excellent linear dichroism. Based on the structural and magnetic measurements, the power loss for the magnetic nanoparticles under study is evaluated over a range of radiofrequencies.

Transverse dipole spin modes in quantum dots

We have carried out a systematic analysis of the transverse dipole spin response of a large-size quantum dot within time-dependent current density functional theory. Results for magnetic fields corresponding to integer filling factors are reported, as well as a comparison with the longitudinal dipole spin response. As in the two-dimensional electron gas, the spin response at high-spin magnetization is dominated by a low-energy transverse mode.

Dissipation in quasistatically driven disordered systems

This work presents an analysis of hysteresis and dissipation in quasistatically driven disordered systems. The study is based on the random field Ising model with fluctuationless dynamics. It enables us to sort out the fraction of the energy input by the driving field stored in the system and the fraction dissipated in every step of the transformation. The dissipation is directly related to the occurrence of avalanches, and does not scale with the size of Barkhausen magnetization jumps. In addition, the change in magnetic field between avalanches provides a measure of the energy barriers between consecutive metastable states

Entropy change and magnetocaloric effect in Gd5(SixGe1-x)4

Isothermal magnetization curves up to 23 T have been measured in Gd5Si1.8Ge2.2. We show that the values of the entropy change at the first-order magnetostructural transition, obtained from the Clausius-Clapeyron equation and the Maxwell relation, are coincident, provided the Maxwell relation is evaluated only within the transition region and the maximum applied field is high enough to complete the transition. These values are also in agreement with the entropy change obtained from differential scanning calorimetry. We also show that a simple phenomenological model based on the temperature and field dependence of the magnetization accounts for these results.

Finite-size scaling analysis of the avalanches in the three-dimensional Gaussian random-field Ising model with metastable dynamics

A numerical study is presented of the third-dimensional Gaussian random-field Ising model at T=0 driven by an external field. Standard synchronous relaxation dynamics is employed to obtain the magnetization versus field hysteresis loops. The focus is on the analysis of the number and size distribution of the magnetization avalanches. They are classified as being nonspanning, one-dimensional-spanning, two-dimensional-spanning, or three-dimensional-spanning depending on whether or not they span the whole lattice in different space directions. Moreover, finite-size scaling analysis enables identification of two different types of nonspanning avalanches (critical and noncritical) and two different types of three-dimensional-spanning avalanches (critical and subcritical), whose numbers increase with L as a power law with different exponents. We conclude by giving a scenario for avalanche behavior in the thermodynamic limit.

Disorder-induced critical phenomena in magnetically glassy Cu-Al-Mn alloys

Measurements of magnetic hysteresis loops in Cu-Al-Mn alloys of different Mn content at low temperatures are presented. The loops are smooth and continuous above a certain temperature, but exhibit a magnetization discontinuity below that temperature. Scaling analysis suggest that this system displays a disorder-induced phase transition line. Measurements allow one to determine the critical exponents ß=0.03±0.01 and ß¿=0.4±0.1, which coincide with those reported recently in a different system, thus supporting the existence of universality for disorder-induced critical points.

Precursor nanoscale modulations in ferromagnets: Modeling and thermodynamic characterization

Using a Ginzburg-Landau model for the magnetic degrees of freedom with coupling to disorder, we demonstrate through simulations the existence of stripelike magnetic precursors recently observed in Co-Ni-Al alloys above the Curie temperature. We characterize these magnetic modulations by means of the temperature dependence of local magnetization distribution, magnetized volume fraction, and magnetic susceptibility. We also obtain a temperature-disorder strength phase diagram in which a magnetic tweed phase exists in a small region between the paramagnetic and dipolar phases.