Síntese e caracterizações estrutural e magnética das ferritas de cobalto-manganês (Co1-xMnxFe2O4 E Co1,2Fe1,8-xMnxO4)

The cobalt-manganese ferrites (Co1¡xMnxFe2O4 and Co1,2Fe1,8¡xMnxO4) has a mixed structure of spinel type and it has been regarded as one of candidates for petitive wide variety of applications in devices from ultrasonic generation and detection, sensors, transformers, as well as in medical industry. Ferrites cobalt-manganese nanostructured were produced via mechanical alloying with subsequent heat treatment and were characterized by X-ray diffraction, X-ray fluorescence, scanning electron microscopy and magnetization. Samples of Co1¡xMnxFe2O4 and Co1,2Fe1,8¡xMnxO4 were obtained from the precursor powders Fe3O4, Co3O4 and Mn3O4 which were stoichiometrically mixed and ground by 10h and heat treated at 900°C for 2h. The diffraction confirmed the formation of the pure nanocrystalline phases to series Co1,2Fe1,8¡xMnxO4 with an average diameter of about 94nm. It was found that the lattice parameter increases with the substitution of Fe3Å by Mn3Å. The x-ray fluorescence revealed that the portions of metals in samples were close to the nominal stoichiometric compositions. The microstructural features observed in micrographs showed that the particles formed show very different morphology and particle size. The magnetic hysteresis measurements performed at low temperature showed that the saturation magnetization and remanence increased as the concentration of manganese, while the coercive field decreased. The anisotropy constant (Ke f ), was estimated from the data adjustments the law of approaching saturation. It was found that the anisotropy decreases substantially with the substitution of Fe by Mn.

Phase diagram and influence of defects in the double perovskites

The phase diagram of the double perovskites of the type Sr_(2-x)La_(x)FeMoO_(6) is analyzed, with and without disorder due to antisites. In addition to an homogeneous half metallic ferrimagnetic phase in the absence of doping and disorder, we find antiferromagnetic phases at large dopings, and other ferrimagnetic phases with lower saturation magnetization, in the presence of disorder.

Large magnetoelectric coupling in nanoscale BiFeO3 from direct electrical measurements

We report the results of direct measurement of remanent hysteresis loops on nanochains of BiFeO3 at room temperature under zero and ∼20 kOe magnetic field. We noticed a suppression of remanent polarization by nearly ∼40% under the magnetic field. The powder neutron diffraction data reveal significant ion displacements under a magnetic field which seems to be the origin of the suppression of polarization. The isolated nanoparticles, comprising the chains, exhibit evolution of ferroelectric domains under dc electric field and complete 180 switching in switching-spectroscopy piezoresponse force microscopy. They also exhibit stronger ferromagnetism with nearly an order of magnitude higher saturation magnetization than that of the bulk sample. These results show that the nanoscale BiFeO3 exhibits coexistence of ferroelectric and ferromagnetic order and a strong magnetoelectric multiferroic coupling at room temperature comparable to what some of the type-II multiferroics show at a very low temperature.

Magnetic analyses of ODP Hole 119-738B sediments

Magnetotactic bacteria intracellularly biomineralize magnetite of an ideal grain size for recording palaeomagnetic signals. However, bacterial magnetite has only been reported in a few pre-Quaternary records because progressive burial into anoxic diagenetic environments causes its dissolution. Deep-sea carbonate sequences provide optimal environments for preserving bacterial magnetite due to low rates of organic carbon burial and expanded pore-water redox zonations. Such sequences often do not become anoxic for tens to hundreds of metres below the seafloor. Nevertheless, the biogeochemical factors that control magnetotactic bacterial populations in such settings are not well known. We document the preservation of bacterial magnetite, which dominates the palaeomagnetic signal throughout Eocene pelagic carbonates from the southern Kerguelen Plateau, Southern Ocean. We provide evidence that iron fertilization, associated with increased aeolian dust flux, resulted in surface water eutrophication in the late Eocene that controlled bacterial magnetite abundance via export of organic carbon to the seafloor. Increased flux of aeolian iron-bearing phases also delivered iron to the seafloor, some of which became bioavailable through iron reduction. Our results suggest that magnetotactic bacterial populations in pelagic settings depend crucially on particulate iron and organic carbon delivery to the seafloor.

Rockmagnetic investigations of IODP Site U1302-U1303

Integrated Ocean Drilling Program (IODP) Sites U1302-U1303, drilled on the SE flank of Orphan Knoll (Labrador Sea), preserve a record of detrital layers and other proxies of hydrographic change that extend the record of ice-sheet/ocean interactions through most of the Brunhes Chron. The age model is built by tandem matching of relative paleointensity (RPI) and oxygen isotope data (d18O) from Neogloboquadrina pachyderma (sin.) to reference records, indicating a mean Brunhes sedimentation rate of 14 cm/kyr. Sedimentation back to marine isotope stage (MIS) 18 is characterized by detrital layers that are detected by higher than background gamma-ray attenuation (GRA) density, peaks in X-ray fluorescence (XRF) indicators for detrital carbonate (Ca/Sr) and detrital silicate (Si/Sr), and an ice-rafted debris (IRD) proxy (wt.% >106 µm). The age model enables correlation of Site U1302/03 to IODP Site U1308 in the heart of the central Atlantic IRD belt where an age model and a similar set of detrital-layer proxies have already been derived. Ages of Heinrich (H) layers H1, H2, H4, H5 and H6 are within ~2 kyr at the two sites (H0, H3 and H5a are not observed at Site U1308), and agree with previous work at Orphan Knoll within ~3 kyr. At Site U1308, Brunhes detrital layers are restricted to peak glacials and glacial terminations back to marine isotope stage (MIS) 16 and have near-synchronous analogs at Site U1302/03. Detrital layers at Site U1302/03 are distributed throughout the record in both glacial and most interglacial stages. We distinguish Heinrich-like layers associated with IRD from detrital layers marked by multiple detrital-layer proxies (including Ca/Sr) but usually not associated with IRD, that may be attributed to lofted sediment derived from drainage and debris-flow events funneled down the nearby Northwest Atlantic Mid-Ocean Channel (NAMOC). The prominent detrital layers at Sites U1302/03 and U1308 can be correlated to millennial scale features in the Chinese speleothem (monsoon) record over the last 400 kyr, implying a link between monsoon precipitation and Laurentide Ice Sheet (LIS) instability. The detrital-layer stratigraphy at Site U1302/03 provides a long record of LIS dynamics against which other terrestrial and marine records can be compared.

Magnetic and petrographic properties of ODP Site 120-747 (Table 1)

Carbonate sediments from the Kerguelen Plateau (ODP Leg 120) of Eocene to Pliocene age were investigated with rock magnetic, petrographic and geochemical methods to determine the carriers of remanent magnetization. Magnetic methods showed that the major magnetic minerals were titanomagnetites slightly larger than single domain particles. Submicrometre to micrometre-size grains of titanomagnetite were identified as inclusions in volcanic glass particles or as crystals in lithic clasts. Volcanic fallout ash particles formed the major fraction of the magnetic extract from each sediment sample. Three groups of volcanic ashes were identified: trachytic ashes, basaltic ashes with sideromelane and tachylite shards, and palagonitic ashes. These three groups could be equally well defined based on their magnetic hysteresis properties and alternating field demagnetization curves. The highest coercivities of all samples were found for the tachylite, due to the submicrometre-size titanomagnetite inclusions in the matrix. Trachytic ashes had intermediate magnetic properties between the single-domain-type tachylites and the palagonitic (altered) basaltic ashes with low coercivities. Samples which contained mixtures of these different volcanic ashes could be distinguished from the three types of ashes based on their magnetic characteristics. There was neither evidence of biogenic magnetofossils in the transmission electron micrographs nor did we find magnetic particles derived from continental Antarctica. The presence of dispersed volcanic fallout ashes between visible ash layers suggests continuous explosive volcanic activity on the Kerguelen Plateau in the South Indian Ocean since the early Eocene. The continuous fallout of volcanic ash from explosive volcanism on the Kerguelen Archipelago is the source of the magnetic particles and thus responsible for the magnetostratigraphy of the nannofossil oozes drilled during Leg 120.

(Table T2) Rock magnetic parameters of ODP Leg 180 sites

Rock magnetic measurements were performed on sediments above 20 meters below seafloor (mbsf) (general) and above 2.5 mbsf (detailed) at Sites 1109, 1110, and 1115 (Ocean Drilling Program Leg 180) in the western Woodlark Basin. Rock magnetic parameters imply the presence of magnetite as a principal magnetic mineral in the sediments. The hysteresis ratios lay in the pseudo-single domain field and generally showed the trend close to that for the mixture of single domain and multidomain magnetite The sediments in the oxidized zones at the top at Sites 1109 and 1115 provided a different trend in the logarithmic plot of the hysteresis ratios, and the oxidized samples were characterized by higher coercivity.

Magnetic properties of the oceanic igneous rocks (Table 1)

Hysteresis measurements have been carried out on a suite of ocean-floor basalts with ages ranging from Quaternary to Cretaceous. Approximately linear, yet separate, relationships between coercivity (Bc) and the ratio of saturation remanence/saturation magnetization (Mrs/Ms) are observed for massive doleritic basalts with low-Ti magnetite and for pillow basalts with multi-domain titanomagnetites (with x= 0.6). Even when the MORB has undergone lowtemperature oxidation resulting in titanomaghemite, the parameters are still distinguishable, although offset from the trend for unoxidized multidomain titanomagnetite. The parameters for these iron oxides with different titanium content reveal contrasting trends that can be explained by the different saturation magnetizations of the mineral types. This plot provides a previously underutilized and non-destructive method to detect the presence of low-titanium magnetite in igneous rocks, notably MORB.

Mineralogical, geochemical and magnetic signatures of surface sediments from the Canadian Beaufort Shelf and Amundsen Gulf (Canadian Arctic)

Mineralogical, geochemical, magnetic, and siliciclastic grain-size signatures of 34 surface sediment samples from the Mackenzie-Beaufort Sea Slope and Amundsen Gulf were studied in order to better constrain the redox status, detrital particle provenance, and sediment dynamics in the western Canadian Arctic. Redox-sensitive elements (Mn, Fe, V, Cr, Zn) indicate that modern sedimentary deposition within the Mackenzie-Beaufort Sea Slope and Amundsen Gulf took place under oxic bottom-water conditions, with more turbulent mixing conditions and thus a well-oxygenated water column prevailing within the Amundsen Gulf. The analytical data obtained, combined with multivariate statistical (notably, principal component and fuzzy c-means clustering analyses) and spatial analyses, allowed the division of the study area into four provinces with distinct sedimentary compositions: (1) the Mackenzie Trough-Canadian Beaufort Shelf with high phyllosilicate-Fe oxide-magnetite and Al-K-Ti-Fe-Cr-V-Zn-P contents; (2) Southwestern Banks Island, characterized by high dolomite-K-feldspar and Ca-Mg-LOI contents; (3) the Central Amundsen Gulf, a transitional zone typified by intermediate phyllosilicate-magnetite-K-feldspar-dolomite and Al-K-Ti-Fe-Mn-V-Zn-Sr-Ca-Mg-LOI contents; and (4) mud volcanoes on the Canadian Beaufort Shelf distinguished by poorly sorted coarse-silt with high quartz-plagioclase-authigenic carbonate and Si-Zr contents, as well as high magnetic susceptibility. Our results also confirm that the present-day sedimentary dynamics on the Canadian Beaufort Shelf is mainly controlled by sediment supply from the Mackenzie River. Overall, these insights provide a basis for future studies using mineralogical, geochemical, and magnetic signatures of Canadian Arctic sediments in order to reconstruct past variations in sediment inputs and transport pathways related to late Quaternary climate and oceanographic changes.

POLYMER-NANOPARTICLE COMPOSITES FOR APPLICATIONS IN FLEXIBLE ELECTRONICS

The aim of this dissertation was to investigate flexible polymer-nanoparticle composites with unique magnetic and electrical properties. Toward this goal, two distinct projects were carried out. The first project explored the magneto-dielectric properties and morphology of flexible polymer-nanoparticle composites that possess high permeability (µ), high permittivity (ε) and minimal dielectric, and magnetic loss (tan δε, tan δµ). The main materials challenges were the synthesis of magnetic nanoparticle fillers displaying high saturation magnetization (Ms), limited coercivity, and their homogeneous dispersion in a polymeric matrix. Nanostructured magnetic fillers including polycrystalline iron core-shell nanoparticles, and constructively assembled superparamagnetic iron oxide nanoparticles were synthesized, and dispersed uniformly in an elastomer matrix to minimize conductive losses. The resulting composites have demonstrated promising permittivity (22.3), permeability (3), and sustained low dielectric (0.1), magnetic (0.4) loss for frequencies below 2 GHz. This study demonstrated nanocomposites with tunable magnetic resonance frequency, which can be used to develop compact and flexible radio frequency devices with high efficiency. The second project focused on fundamental research regarding methods for the design of highly conductive polymer-nanoparticle composites that can maintain high electrical conductivity under tensile strain exceeding 100%. We investigated a simple solution spraying method to fabricate stretchable conductors based on elastomeric block copolymer fibers and silver nanoparticles. Silver nanoparticles were assembled both in and around block copolymer fibers forming interconnected dual nanoparticle networks, resulting in both in-fiber conductive pathways and additional conductive pathways on the outer surface of the fibers. Stretchable composites with conductivity values reaching 9000 S/cm maintained 56% of their initial conductivity after 500 cycles at 100% strain. The developed manufacturing method in this research could pave the way towards direct deposition of flexible electronic devices on any shaped substrate. The electrical and electromechanical properties of these dual silver nanoparticle network composites make them promising materials for the future construction of stretchable circuitry for displays, solar cells, antennas, and strain and tactility sensors.

CONTROL OF SIZE AND MAGNETIC PROPERTIES OF CARBOXYL-FUNCTIONALIZED MAGNETITE PARTICLES: SYNTHESIS PROCEDURES, CHARACTERIZATIONS, AND APPLICATIONS

Magnetic nanoparticles (MNPs) are known for the unique properties conferred by their small size and have found wide application in food safety analyses. However, their high surface energy and strong magnetization often lead to aggregation, compromising their functions. In this study, iron oxide magnetic particles (MPs) over the range of nano to micro size were synthesized, from which particles with less aggregation and excellent magnetic properties were obtained. MPs were synthesized via three different hydrothermal procedures, using poly (acrylic acid) (PAA) of different molecular weight (Mw) as the stabilizer. The particle size, morphology, and magnetic properties of the MPs from these synthesis procedures were characterized and compared. Among the three syntheses, one-step hydrothermal synthesis demonstrated the highest yield and most efficient magnetic collection of the resulting PAA-coated magnetic microparticles (PAA-MMPs, >100 nm). Iron oxide content of these PAA-MMPs was around 90%, and the saturation magnetization ranged from 70.3 emu/g to 57.0 emu/g, depending on the Mw of PAA used. In this approach, the particles prepared using PAA with Mw of 100K g/mol exhibited super-paramagnetic behavior with ~65% lower coercivity and remanence compared to others. They were therefore less susceptible to aggregation and remained remarkably water-dispersible even after one-month storage. Three applications involving PAA-MMPs from one-step hydrothermal synthesis were explored: food proteins and enzymes immobilization, antibody conjugation for pathogen capture, and magnetic hydrogel film fabrication. These studies demonstrated their versatile functions as well as their potential applications in the food science area.

Efeito da moagem de alta energia na microestrutura e nas propriedades magnéticas do compósito wc-10%p.Co

This work a studied the high energy milling effect in microstructure and magnetic properties of the WC-10wt.%Co composite. The composite powders were prepared by mechanical mixed and milled at 2 hours, 100 hours, 200 hours and 300 hours in planetary milling. After this process the composite were compacted in stainless steel die with cylindrical county of 10 mm of diameter, at pressure 200 Mpa and sintered in a resistive furnace in argon atmosphere at 1400 oC for 5 min. The sintered composite were cutted, inlaid, sandpapered, and polished. The microestrutural parameters of the composite was analyzed by X-ray diffraction, scanning electronic microscopy, optical microscopy, hardness, magnetic propriety and Rietveld method analyze. The results shows, with milling time increase the particle size decrease, it possibility minor temperature of sintering. The increase of milling time caused allotropic transformation in cobalt phase and cold welding between particles. The cold welding caused the formation of the particle composite. The X-ray diffraction pattern of composite powders shows the WC peaks intensity decrease with the milling time increase. The X-ray diffraction pattern of the composite sintered samples shows the other phases. The magnetic measurements detected a significant increase in the coercitive field and a decrease in the saturation magnetization with milling time increase. The increase coercitive field it was also verified with decrease grain size with milling time increase. For the composite powders the increase coercitive field it was verified with particle size reduction and saturation magnetization variation is relate with the variation of free cobalt. The Rietveld method analyze shows at milling time increase the mean crystalline size of WC, and Co-cfc phases in composite sintered sample are higher than in composite powders. The mean crystallite size of Co-hc phase in composite powders is higher than in composite sintered sample. The mean lattice strains of WC, Co-hc and Co-cfc phases in composite powders are higher than in composite sintered samples. The cells parameters of the composite powder decrease at milling time increase this effect came from the particle size reduction at milling time increase. In sintered composite the cells parameters is constant with milling time increase