Multifunctional polymer nanocomposites (PNCs) are attractive for the design of tunable RF and microwave components such as flexible electronics, attenuators, and antennas due to cost-effectiveness and durability of polymeric matrices. In this work, three separate PNCs were synthesized. Magnetite (Fe3O4) and cobalt ferrite (CFO) nanoparticles, synthesized by thermal decomposition, were used as PNC fillers. Polymers used in this work were a commercial polymer provided by the Rogers Corporation (RP) and polyvinylidene fluoride (PVDF). PNCs in this thesis consist of Fe3O4 in RP, CFO in RP, and Fe3O4 in PVDF. Characterization techniques for determining morphology of the nanoparticles, and their resulting PNCs, include x-ray diffraction, transmission electron microscopy and magnetometry. All magnetometry measurements were taken using a Quantum Design Physical Property Measurement System with a superconducting magnet. Temperature and external magnetic field magnetization measurements revealed that all samples exhibit superparamagnetic behavior at room temperature. Blocking temperature, coercivity and reduced remnant magnetization do not vary with concentration. Tunable saturation magnetization, based on nanoparticle loading, was observed across all PNCs, regardless of polymer or nanoparticle choice, indicating that this is an inherent property in all similar PNC materials. Tunability studies of the magneto-dielectric PNCs were carried out by adding the PNC to cavity and microstrip linear resonator devices, and passing frequencies of 1-6 GHz through them in the presence of transverse external magnetic fields of up to 4.5 kOe, provided by an electromagnet. Microwave characteristics were extracted from scattering parameters of the PNCs. In all cases, losses were reduced, quality factor was increased, and tunability of the resonance frequency was demonstrated. Strong magnetic field dependence was observed across all samples measured in this study.

No description available.

We present a study of the synthesis, structural and magnetic properties of bulk and nanosized (Zn, Cd, Cu)0:5Ni0:5Fe2O4 and NiFe2O4 compounds. The e®ects of electronic con¯guration and atomic sizes of Zn, Cd, Cu and Ni on the magnetic properties of the ferrites are the primary focus of the study. Di®erent synthesis routes, preparation conditions and how they a®ect single phase formation are explored. The synthesis was undertaken by solid{state reaction, combustion, hydrothermal and glycothermal techniques. The structure determination was by Xray di®raction. The magnetic measurements were performed using MÄossbauer spectroscopy (from 79 K to about 850 K) and a vibrating sample magnetometer (at about 300 K). The bulk densities of the sintered pellets were deduced by Archimedes principle. The bulk oxides were produced by solid{state reaction and combustion techniques. Fine powders with grain sizes of about 10 nm were produced from bulk compounds by a Retsch planetary ball mill and by the hydrothermal and glycothermal processes. The e®ects of the applied pressure used to make pellets (related to green density of the raw pellets) and the sintering temperature on the properties were investigated. An anomalous variation of bulk densities of (Zn, Cd)0:5Ni0:5Fe2O4 oxides with increase in pelletizing pressure was observed which appears to suggest evidence for trapped porosity. Di®erent states of pelletizing the samples appear to be related to a systematic change of the hyper¯ne ¯eld distributions derived from the MÄossbauer spectra. The temperature dependence of the magnetic hyper ¯ne ¯elds at tetrahedral (A) and octahedral (B) sites were observed to vary with temperature according to the equations Bhf (T) = Bhf (0)[1 ¡ (T=TC)n]¯n where n = 1 (based on the Landau{Ginzburg theory) and n = 2 (based on the Stoner theory). The equation Bhf (T) = Bhf (0)[1¡(T=TC)2]¯2 appears to ¯t the hyper¯ne ¯eld data over a wider temperature range. The Zn{ and Cd{based oxides were found to be ferrimagnetic with Curie temperature TC = 548 § 3 K (measured by zero velocity technique). The Cu{based compound exhibited antiferromagnetic behavior with a magnetic transition temperature of 825 § 3 K. The di®erence in behavior between Zn{, Cd{ and Cu{based compounds is due to di®erence in electronic con¯guration and atomic or ionic sizes. The stronger magnetic coupling between spins in the Cu{based sample can be explained by the presence of RKKY interactions in addition to superexchange interactions. The larger ionic size for Cd appears to favour smaller grain sizes in Cd{based oxides. An anomalous increase in TC is obtained in the Zn0:5Ni0:5Fe2O4 compound with reduction in grain size. This increase in TC is attributed to a distribution of Zn ions on both A and B sites. The MÄossbauer spectra of the milled nanosized samples show a combination of ferrimagnetic and paramagnetic behavior. The coercive ¯eld (HC) at room temperature was found to increase with reduction in grain size (G) according to the equation HC = am+bm=G, which is consistent with multidomain particles. With further reduction in grain sizes, the coercive ¯eld reduced according to the equation HC = as ¡bs=G2. This equation is associated with the onset of single domain particles. The samples produced by hydrothermal and glycothermal processes show evidence of transformation from single domain to multidomain structure with increasing sintering temperature. The ease of single{phase formation in the compounds studied is shown to depend on the technique used to prepare the samples. Single phase formation of the spinel structure was easier to achieve in samples prepared by wet chemical methods because lower sintering temperatures (T < 1000 oC) were required. / Thesis (Ph.D.)-University of KwaZulu-Natal, Westville, 2007.

The synthesis, structure and physical properties of a series of Mnx(Co, Mg)₁ˍxFe₂O₄, (Mg, Sr)₀.₂ Mn₀.₁Co₀.₇Fe₂O₄ and Mg₀.₅Mn₀.₅(RE)₀.₁Fe₁.₉O₄ (where RE are rare earth elements) nanoferrites have been studied. These compounds were synthesized at low reaction temperature of about 200 ⁰C using the glycol-thermal method. The starting materials were high-purity metal chlorides or nitrates which were precipitated by NH₄OH and KOH respectively. In addition, MnxCo₁₋xFe₂O₄ (x = 0, 0.5 and 1) samples were produced directly from high-purity metal oxides by high-energy ball milling technique. Single-phase cubic spinel structure and nanoparticle structure of the synthesized samples were confirmed by X-ray diffraction (XRD) and transmission electron microscope (TEM). The results show that the produced powders of the asprepared samples have average grain sizes ranging from 7 to 16 nm. Filtering the precipitates by Whatman glass microfiber filters (GF/F) appears to be important in obtaining the small particle sizes. We suspect higher stability of the MnxCo₁₋xFe₂O₄ at x = 0 and 0.5 where complete symmetry in the proportion of the atoms on tetrahedral (A) and octahedral (B) sites would tend to favour larger nanoparticles. The evolutions of the magnetic properties as a function of composition, annealing temperature under air and argon atmospheres or measuring temperature have been investigated by ⁵⁷Fe Mössbauer spectroscopy, vibration sample magnetometer (VSM) and superconducting quantum interference device (SQUID). Significant changes in magnetic properties are observed across the composition ranges studied. The Mössbauer spectra indicate ferrimagnetic, superparamagnetic and paramagnetic behaviours of the compounds. The results show evidence of transformation from single-domain to multi-domain structure with thermal annealing in our samples. Temperature dependence of magnetization shows differences between field cooling (FC) and zero field cooling (ZFC) which we attribute to spin-freezing and thermal relaxation for typical nanoparticles. Significant increase in coercive field with reduction in measuring temperature is obtained in Co- based compounds. Mn₀.₅Co₀.₅Fe₂O₄, Sr₀.₂Mn₀.₁Co₀.₇Fe₂O₄ and Mg₀.₂Mn₀.₁Co₀.₇Fe₂O₄ have large coercive fields of 1.45, 3.02 and 10.70 kOe at 4 K compared to 0.17, 0.05 and 0.05 kOe at room temperature respectively. Variation of coercive fields (Hc) with measuri ing temperature for MnxCo₁₋xFe₂O₄ (x = 0.1 and 0.05), (Mg, Sr)₀.₂Mn₀.₁Co₀.₇Fe₂O₄ nanoferrites follow the Kneller's law for uniaxial non-interacting single domain particles of the form Hc(T) = Hc(0)[1-( T/Tβ)α]. The observed temperature dependences are consistent with α = 1/2. We also find evidence of the departure from this law at lower temperature. The temperature dependence of the saturation magnetizations were observed to vary with temperature according to the modified Bloch's law Ms(T) = Ms(0)[1 - ( T/T₀)ᵝ] where β is at least 1.5. This is attributed to the confinement effects of the spin-wave spectrum for magnetic clusters. The equation appears to fit the saturation magnetization data over the entire temperature range with values of β from 2.1 to 2.4 for the samples studied. These results are consistent with the nanoparticle nature of the compounds. In Mg₀.₅Mn₀.₅(RE)₀.₁Fe₁.₉O₄ nanoferrites, the grain sizes, lattice parameters and saturation magnetizations increase with RE substitution which we attribute to larger RE ions substituting smaller Fe ions. The results show evidence of superparamagnetic behaviour of the nanoparticles. The highest grain size and magnetizations are obtained for the Gd substituted sample. We find strong correlation between the saturation magnetizations, grain sizes and microstrains with de Gennes factor G. The correlation with grain sizes and microstrains appear to be unique and characteristic of the nanoparticle nature of the compounds. Bulk samples in the form of pellets were also produced from the as-prepared samples of MnxCo₁₋xFe₂O₄ for resistivity measurements. The temperature dependence of the electrical resistivity for samples sintered from 600 - 1100 ⁰C under argon atmosphere were studied using the four-probe method from room temperature to about 110 ⁰C. Two possible mechanisms for resistivity involving Tˉ¹ and Tˉ¹/² dependences were investigated which we associated with semiconducting and inter-grain conductivity respectively. The Tˉ¹/² dependence is found to fit the data better and predicts higher activation energies. The resistivity was observed to be sensitive to the surface of the pellet being probed and the annealing temperature. / Thesis (Ph.D.)-University of KwaZulu-Natal, Durban, 2012.

The magnetic spinel ferrite nanoparticle is exceptionally intriguing nanocrystal system due to the industrial importance of various technical applications and the scientific significance of studying the quantum origin of magnetism. Studies of quantum influences upon magnetic properties have revealed that the spin-orbit coupling and the net magnetization greatly affect the net magnetic properties of each spinel ferrite system differently. In case of cobalt ferrite where spin-orbit coupling is relatively large, increasing Cr3+ doping concentration, which has smaller magnetic moment and zero angular moment, decreases blocking temperature, saturation magnetization, remnant magnetization and coercivity. However, in case of manganese ferrite where spin-orbit coupling is relatively small, increasing Cr3+ doping concentration, reduces all the magnetic parameters except coercivity. The coercivity increases due to smaller magnetocrystalline anisotropy energy constant which forces the coercivity to increase as saturation magnetization decreases in accordance with Stoner-Wohlfarth theory. In order to improve product quality and quantity, synthesis routes in hot oleylamine and aminolytic reaction were developed. Both methods were proven to be extremely effective, environmental friendly, inexpensive, and simple routes in the synthesis of a variety of spinel ferrite systems including CoFe2O4, MnFe2O4, NiFe2O4, and ZnFe2O4 from a single source metal precursor.

Thesis (M.S.)--University of Texas at El Paso, 2009. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

Thesis (M.S.)--Missouri University of Science and Technology, 2009. / Vita. The entire thesis text is included in file. Title from title screen of thesis/dissertation PDF file (viewed November 17, 2009) Includes bibliographical references (p. 83-84).

This work presents the preparation and physical properties of spinel nanoparticles and nanocomposites. All nanocomposites in diamagnetic matrix like chromites CoCr2O4, CuCr2O4, NiCr2O4, ZnCr2O4 and ferrite MgFe2O4 were prepared using sol-gel method. On the other hand, isolated nanoparticles such as MgCr2O4, MnCr2O4, CuCr2O4, NiCr2O4, and FeCr2O4, were prepared using autocombustion a co-precipitation methods. CoFe2O4 and MgFe2O4 were prepared by microemulsion alkoxide method. This microemulsion method was used for the spinel nanoparticles preparation for the first time. This work describes the influence of heat treatment temperature on the final particle size and influence of particle size on physical properties of material. The study of the influence of twovalent cationt in the spinel structure on the magnetic properties of chromites was also carried out. The final samples were characterized by XRD powder diffraction, Mössbauer spectroscopy, infrared and Raman spectroscopy, and HRTEM. The dependence of magnetization on applied magnetic field at constant temperature and ZFC (zero-field cooling) - FC (field cooling) measurement was carried out on the prepared sample.

No description available.

Nos objectifs sont ici de comprendre comment les propriétés magnétiques de nanoparticules (NPs) sont affectées par la diminution de leur taille et par leur composition chimique, et comprendre ce qui régit leur mouvement thermophorétique et l'effet magnéto-calorique. Des ferrofluides composés de NPs de structure cœur-couronne sont synthétisés ici avec un cœur de ferrite de Mn, de Co ou de ferrite mixte Zn-Mn, recouvert d'une couronne de maghémite. Les mesures magnétiques révèlent une composition magnétique mixte conduisant à l'observation d'un exchange bias qui se manifeste par des cycles d'hystérésis décalés à basses températures. Nous comparons ce phénomène dans le cas de NPs à cœur magnétiquement dur (CoFe2O4) et à cœur magnétiquement mou (MnFe2O4). Indépendamment de la nature du cœur, ce champ d'échange augmente jusqu'à un maximum, obtenu quand le champ de refroidissement est de l'ordre de la moitié du champ d'anisotropie. Les propriétés thermophorétiques des dispersions, sondées par diffusion Rayleigh forcée, sont gouvernées par la physico-chimie du colloïde (ligand de surface, contre-ions, interactions entre NPs) indépendamment de la composition chimique et des propriétés magnétiques en champ nul. Le coefficient Soret est ici négatif (NPs thermophiles) et est relié à la compressibilité osmotique donnée par un formalisme de Carnahan-Starling effectif. On modélise la friction en régime dilué par la loi d'Einstein et en régime concentré, à l'approche de la transition vitreuse, par un modèle de Vogel-Fulcher. Les mesures de l’effet magnéto-calorique démontrent une similarité avec les matériaux commerciaux, avec une forte influence de la composition chimique du cœur. / Our objective is to understand how the magnetic properties of nanoparticles (NPs) can be affected by their size reduction and their chemical composition, and also to determine their role on their thermophoretic motion and on the magneto-caloric effect. For this purpose, aqueous ferrofluids are synthesized with core-shell NPs based on a core of Mn-ferrite, Co-ferrite and mixed Zn-Mn ferrites, coated with a maghemite shell. The magnetic measurements evidence a ferrimagnetic core, covered with disordered frozen spins (SGL), driving an exchange bias phenomenon shifting the hysteresis loops, when the system is cooled under a field Hfc. This exchange bias is measured as a function of Hfc, in samples with NPs having either a hard (CoFe2O4) or a soft (MnFe2O4) magnetic core. Whatever the nature of the magnetic core, the exchange bias field grows up to reach a maximum, always found at Hfc of the order of half of the anisotropy field. The thermophoretic properties of the dispersions, probed by Forced Rayleigh Scattering, are ruled by colloidal physico-chemical features (surface ligand, counter ions, interparticle interactions) whatever the chemical composition and the magnetic properties in zero magnetic field. The Soret coefficient is found here negative (thermophilic NPs) and is related to the osmotic compressibility, modeled by an effective Carnahan-Staring formalism. In the dilute regime, the friction follows an Einstein law, while a Vogel-Fulcher formalism describes the concentrated regime, at the approach of the glass transition. The magneto-caloric measurements demonstrate a similarity with commercial materials. They are strongly influenced by the core composition.