Grain entrainment and transport rates of magnetic minerals of coastal sediment samples from the Bay of Plenty, New Zealand

Heavy (magnetic & non-magnetic) minerals are found concentrated by natural processes in many fluvial, estuarine, coastal and shelf environments with a potential to form economic placer deposits. Understanding the processes of heavy mineral transport and enrichment is prerequisite to interpret sediment magnetic properties in terms of hydro- and sediment dynamics. In this study, we combine rock magnetic and sedimentological laboratory measurements with numerical 3D discrete element models to investigate differential grain entrainment and transport rates of magnetic minerals in a range of coastal environments (riverbed, mouth, estuary, beach and near-shore). We analyzed grain-size distributions of representative bulk samples and their magnetic mineral fractions to relate grain-size modes to respective transport modes (traction, saltation, suspension). Rock magnetic measurements showed that distribution shapes, population sizes and grain-size offsets of bulk and magnetic mineral fractions hold information on the transport conditions and enrichment process in each depositional environment. A downstream decrease in magnetite grain size and an increase in magnetite concentration was observed from riverine source to marine sink environments. Lower flow velocities permit differential settling of light and heavy mineral grains creating heavy mineral enriched zones in estuary settings, while lighter minerals are washed out further into the sea. Numerical model results showed that higher heavy mineral concentrations in the bed increased the erosion rate and enhancing heavy mineral enrichment. In beach environments where sediments contained light and heavy mineral grains of equivalent grain sizes, the bed was found to be more stable with negligible amount of erosion compared to other bed compositions. Heavy mineral transport rates calculated for four different bed compositions showed that increasing heavy mineral content in the bed decreased the transport rate. There is always a lag in transport between light and heavy minerals which increases with higher heavy mineral concentration in all tested bed compositions. The results of laboratory experiments were validated by numerical models and showed good agreement. We demonstrate that the presented approach bears the potential to investigate heavy mineral enrichment processes in a wide range of sedimentary settings.

Rock magnetic properties and radiocarbon dates of samples obtained on Ile de Possession, South Indian Ocean

A 6200 year old peat sequence, cored in a volcanic crater on the sub-Antarctic Ile de la Possession (Iles Crozet), has been investigated, based on a multi-proxy approach. The methods applied are macrobotanical (mosses, seeds and fruits) and diatom analyses, complemented by geochemical (Rock-Eval6) and rock magnetic measurements. The chronology of the core is based on 5 radiocarbon dates. When combining all the proxy data the following changes could be inferred. From the onset of the peat formation (6200 cal yr BP) until ca. 5550 cal yr BP, biological production was high and climatic conditions must have been relatively warm. At ca. 5550 cal yr BP a shift to low biological production occurred, lasting until ca. 4600 cal yr BP. During this period the organic matter is well preserved, pointing to a cold and/or wet environment. At ca. 4600 cal yr BP, biological production increased again. From ca. 4600 cal yr BP until ca. 4100 cal yr BP a 'hollow and hummock' micro topography developed at the peat surface, resulting in the presence of a mixture of wetter and drier species in the macrobotanical record. After ca. 4100 cal yr BP, the wet species disappear and a generally drier, acidic bog came into existence. A major shift in all the proxy data is observed at ca. 2800 cal yr BP, pointing to wetter and especially windier climatic conditions on the island probably caused by an intensification and/or latitudinal shift of the southern westerly belt. Caused by a stronger wind regime, erosion of the peat surface occurred at that time and a lake was formed in the peat deposits of the crater, which is still present today.

Thermomagnetic measurements on sediment cores GeoB1523-1, GeoB2910-1 and Geob4313-2

Low-temperature rock magnetic measurements have distinct diagnostic value. However, in most bulk marine sediments the concentration of ferrimagnetic and antiferromagnetic minerals is extremely low, so even sensitive instrumentation often responds to the paramagnetic contribution of the silicate matrix in the residual field of the magnetometer. Analysis of magnetic extracts is usually performed to solve the problems raised by low magnetic concentrations. Additionally magnetic extracts can be used for several other analyses, for example electron microscopy or X-ray diffraction. The magnetic extraction technique is generally sufficient for sediments dominated by magnetite. In this study however, we show that high-coercivity components are rather underrepresented in magnetic extracts of sediments with a more complex magnetic mineralogy. We test heavy liquid separation, using hydrophilic sodium polytungstenate solution Na6[H2W12O40], to demonstrate the efficiencies of both concentration techniques. Low-temperature cycling of zero-field-cooled, field-cooled and saturation isothermal remanent magnetization acquired at room temperature was performed on dry bulk sediments, magnetic extracts, and heavy liquid separates of clay-rich pelagic sediments originating from the Equatorial Atlantic. The results of the thermomagnetic measurements clarify that magnetic extraction favours components with high spontaneous magnetization, such as magnetite and titanomagnetite. The heavy liquid separation is unbiased with respect to high- and low-coercive minerals, thus it represents the entire magnetic assemblage.

Paleomagnetic and rock magnetic characterization of ODP Leg 210 cores

We conducted an integrated paleomagnetic and rock magnetic study on cores recovered from Ocean Drilling Program Sites 1276 and 1277 of the Newfoundland Basin. Stable components of magnetization are determined from Cretaceous-aged sedimentary and basement cores after detailed thermal and alternating-field demagnetization. Results from a series of rock magnetic measurements corroborate the demagnetization behavior and show that titanomagnetites are the main magnetic carrier. In view of the normal polarity of magnetization and radiometric dates for the sills at Site 1276 (~98 and ~105 Ma, both within the Cretaceous Normal Superchron) and for a gabbro intrusion in peridotite at Site 1277 (~126 Ma, Chron M1), our results suggest that the primary magnetization of the Cretaceous rocks is likely retained in these rocks. The overall magnetic inclination of lithologic Unit 2 in Hole 1277A between 143 and 180 meters below seafloor is 38°, implying significant (~35° counterclockwise, viewed to the north) rotation of the basement around a horizontal axis parallel to the rift axis (010°). The paleomagnetic rotational estimates should help refine models for the tectonic evolution of the basement. The mean inclinations for Sites 1276 and 1277 rocks imply paleolatitudes of 30.3° ± 5.1° and 22.9° ± 12.0°, respectively, with the latter presumably influenced by tectonic rotation. These values are consistent with those inferred from the mid-Cretaceous reference poles for North America, suggesting that the inclination determinations are reliable and consistent with a drill site on a location in the North America plate since at least the mid-Cretaceous. The combined paleolatitude results from Leg 210 sites indicate that the Newfoundland Basin was some 1800 km south of its current position in the mid-Cretaceous. Assuming a constant rate of motion, the paleolatitude data would suggest a rate of 12.1 mm/yr for the interval from ~130 Ma (Site 1276 age) to present, and 19.6 mm/yr for the interval from 126 Ma (Site 1277 age) to recent. The paleolatitude and rotational data from this study are consistent with the possibility that Site 1276 may have passed over the Canary and Madeira hotspots that formed the Newfoundland Seamounts in the mid-Cretaceous.

Magnetic field measurement and spectroscopy in multipole fields /

"February 1965."

One- and two-step spin-crossover behavior of [Fe(II)(isoxazole)6]2+ and the structure and magnetic properties of triangular [Fe(III)3O(OAc)6(isoxazole)3][ClO4)]

The structure and spin-crossover magnetic behavior of [FeII16][BF4]2 (1 = isoxazole) and [FeII16][ClO4]2 have been studied. [FeII16][BF4]2 undergoes two reversible spin-crossover transitions at 91 and 192 K, and is the first two-step spin transition to undergo a simultaneous crystallographic phase transition, but does not exhibit thermal hysteresis. The single-crystal structure determinations at 260 [space group P3̄, a = 17.4387(4) Å, c = 7.6847(2) Å] and at 130 K [space group P1̄, a = 17.0901(2) Å, b = 16.7481(2) Å, c = 7.5413(1) Å, α = 90.5309(6)°, β = 91.5231(6)°, γ = 117.8195(8)°] reveal two different iron sites, Fe1 and Fe2, in a 1:2 ratio. The room-temperature magnetic moment of 5.0 μB is consistent with high-spin Fe(II). A plateau in μ(T) having a moment of 3.3 μB centered at 130 K suggests a mixed spin system of some high-spin and some low-spin Fe(II) molecules. On the basis of the Fe−N bond distances at the two temperatures, and the molar fraction of high-spin molecules at the transition plateau, Fe1 and Fe2 can be assigned to the 91 and 192 K transitions, respectively. [FeII16][ClO4]2 [space group P3̄, a = 17.5829(3) Å, c = 7.8043(2) Å, β = 109.820 (3)°, T = 295 K] also possesses Fe1:Fe2 in a 1:2 ratio, and magnetic measurements show a single spin transition at 213 K, indicating that both Fe1 and Fe2 undergo a simultaneous spin transition. [FeII16][ClO4]2 slowly decomposes in solutions containing acetic anhydride to form [FeIII3O(OAc)613][ClO4] [space group I2, a = 10.1547(7) Å, b = 16.5497(11) Å, c = 10.3205(9) Å, β = 109.820 (3)°, T = 200 K]. The isosceles Fe3 unit contains two Fe···Fe distances of 3.2844(1) Å and a third Fe···Fe distance of 3.2857(1) Å. The magnetic data can be fit to a trinuclear model with ℋ = −2J(S1·S2 + S2·S3) − 2J13(S1·S3), where J = −27.1 and J13 = −32.5 cm-1.

(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.

Coupling of magnetic, strain and electric polarization fields in the structure of multiferroic material

The comprehensive study on the coupling of magnetism, electrical polarization and the crystalline lattice with the off-stoichiometric effects in self-doped multiferroic hexagonal h-LuMnxO3±δ (0.92≤x≤1.12) ceramic oxides was carried out for the PhD work. There is a complex coupling of the three ferroic degrees. The cancelation of the magnetic moments of ions in the antiferromagnetic order, electric polarization with specific vortex/antivortex topology and lattice properties have pushed researchers to find out ways to disclose the underlying physics and chemistry of magneto-electric and magneto-elastic couplings of h-RMnO3 multiferroic materials. In this research work, self-doping of Lu-sites or Mn-sites of h-LuMnxO3±δ ceramics prepared via solid state route was done to pave a way for deeper understanding of the antiferromagnetic transition, the weak ferromagnetism often reported in the same crystalline lattices and the ferroelectric properties coupled to the imposed lattice changes. Accordingly to the aim of the PhD thesis, the objectives set for the sintering study in the first chapter on experimental results were two. First, study of sintering off-stoichiometric samples within conditions reported in the bibliography and also extracted from the phase diagrams of the LuMnxO3±δ, with a multiple firings ending with a last high temperature step at 1300ºC for 24 hours. Second, explore longer annealing times of up to 240 hours at the fixed temperature of 1300 ºC in a search for improving the properties of the solid solution under study. All series of LuMnxO3±δ ceramics for each annealing time were characterized to tentatively build a framework enabling comparison of measured properties with results of others available in literature. XRD and Rietveld refinement of data give the evolution the lattice parameters as a function to x. Shrinkage of the lattice parameters with increasing x values was observed, the stability limit of the solid solution being determined by analysis of lattice parameters. The evolution of grain size and presence of secondary phases have been investigated by means of TEM, SEM, EDS and EBSD techniques. The dependencies of grain growth and regression of secondary phases on composition x and time were further characterized. Magnetic susceptibility of samples and magnetic irreversibility were extensively examined in the present work. The dependency of magnetic susceptibility, Neel ordering transition and important magnetic parameters are determined and compared to observation in other multiferroics in the following chapter of the thesis. As a tool of high sensitivity to detect minor traces of the secondary phase hausmannite, magnetic measurements are suggested for cross-checking of phase diagrams. Difficulty of previous studies on interpreting the magnetic anomaly below 43 K in h-RMnO3 oxides was discussed and assigned to the Mn3O4 phase, with supported of the electron microscopy. Magneto-electric coupling where AFM ordering is coupled to dielectric polarization is investigated as a function of x and of sintering condition via frequency and temperature dependent complex dielectric constant measurements in the final chapter of the thesis. Within the limits of solid solubility, the crystalline lattice of off-stoichiometric ceramics was shown to preserve the magneto-electric coupling at TN. It represents the first research work on magneto-electric coupling modified by vacancy doping to author’s knowledge. Studied lattices would reveal distortions at the atomic scale imposed by local changes of x dependent on sintering conditions which were widely inspected by using TEM/STEM methods, complemented with EDS and EELS spectroscopy all together to provide comprehensive information on cross coupling of distortions, inhomogeneity and electronic structure assembled and discussed in a specific chapter. Internal interfaces inside crystalline grains were examined. Qualitative explanations of the measured magnetic and ferroelectric properties were established in relation to observed nanoscale features of h-LuMnxO3±δ ceramics. Ferroelectric domains and topological defects are displayed both in TEM and AFM/PFM images, the later technique being used to look at size, distribution and switching of ferroelectric domains influenced by vacancy doping at the micron scale bridging to complementary TEM studies on the atomic structure of ferroelectric domains. In support to experimental study, DFT simulations using Wien2K code have been carried out in order to interpret the results of EELS spectra of O K-edge and to obtain information on the cation hybridization to oxygen ions. The L3,2 edges of Mn is used to access the oxidation state of the Mn ions inside crystalline grains. In addition, rehybridization driven ferroelectricity is also evaluated by comparing the partial density of states of the orbitals of all ions of the samples, also the polarization was calculated and correlated to the off-stoichiometric effect.

Disentangling the magnetic force noise contribution in LISA Pathfinder

Magnetically-induced forces on the inertial masses on-board LISA Path finder are expected to be one of the dominant contributions to the mission noise budget, accounting for up to 40%. The origin of this disturbance is the coupling of the residual magnetization and susceptibility of the test masses with the environmental magnetic field. In order to fully understand this important part of the noise model, a set of coils and magnetometers are integrated as a part of the diagnostics subsystem. During operations a sequence of magnetic excitations will be applied to precisely determine the coupling of the magnetic environment to the test mass displacement using the on-board magnetometers. Since no direct measurement of the magnetic field in the test mass position will be available, an extrapolation of the magnetic measurements to the test mass position will be carried out as a part of the data analysis activities. In this paper we show the first results on the magnetic experiments during an end-to-end LISA Path finder simulation, and we describe the methods under development to map the magnetic field on-board.

Direct visualization of magnetic-field-induced magnetoelectric switching in multiferroic Aurivillius phase thin films

Multiferroic materials displaying coupled ferroelectric and ferromagnetic order parameters could provide a means for data storage whereby bits could be written electrically and read magnetically, or vice versa. Thin films of Aurivillius phase Bi6Ti2.8Fe1.52Mn0.68O18, previously prepared by a chemical solution deposition (CSD) technique, are multiferroics demonstrating magnetoelectric coupling at room temperature. Here, we demonstrate the growth of a similar composition, Bi6Ti2.99Fe1.46Mn0.55O18, via the liquid injection chemical vapor deposition technique. High-resolution magnetic measurements reveal a considerably higher in-plane ferromagnetic signature than CSD grown films (MS = 24.25 emu/g (215 emu/cm3), MR = 9.916 emu/g (81.5 emu/cm3), HC = 170 Oe). A statistical analysis of the results from a thorough microstructural examination of the samples, allows us to conclude that the ferromagnetic signature can be attributed to the Aurivillius phase, with a confidence level of 99.95%. In addition, we report the direct piezoresponse force microscopy visualization of ferroelectric switching while going through a full in-plane magnetic field cycle, where increased volumes (8.6 to 14% compared with 4 to 7% for the CSD-grown films) of the film engage in magnetoelectric coupling and demonstrate both irreversible and reversible magnetoelectric domain switching.

Magnetostriction of polycrystalline Fe-Ge alloys

The longitudinal and transverse magnetostriction and microstructure of polycrystalline Fe(100-x)Ge(x) (x= 8, 12, 15, 20) alloys were investigated in order to correlate the magnetostriction with microstructure. In order to obtain different microstructures in the Fe(100-x)Ge(x) alloys, the samples were annealed at 600 degrees C during 2 h and at 1150 degrees C for half hour and then quenched in cold water. For Ge concentrations lower than 14 at.%, the longitudinal magnetostriction is positive and increases positively up to 22 ppm at 12 at.% Ge then decreases and vanishes at about 14 at.% Ge. For further Ge concentration increase the longitudinal magnetostriction is negative and reaches -30 ppm for Fe(80)Ge(20). This behavior, that is very similar to that reported for Fe-Si alloys, is explained by the structural changes caused by different thermal histories of the alloys. (C) 2008 Published by Elsevier B. V.

Annealing effects on microstructure and coercive field of ferritic-martensitic ODS Eurofer steel

Oxide dispersion strengthened reduced-activation ferritic-martensitic steels are promising candidates for applications in future fusion power plants. Samples of a reduced activation ferritic-martensitic 9 wt.%Cr-oxide dispersion strengthened Eurofer steel were cold rolled to 80% reduction in thickness and annealed in vacuum for 1 h from 200 to 1350 degrees C to evaluate its thermal stability. Vickers microhardness testing and electron backscatter diffraction (EBSD) were used to characterize the microstructure. The microstructural changes were also followed by magnetic measurements, in particular the corresponding variation of the coercive field (H(c)), as a function of the annealing treatment. Results show that magnetic measurements were sensitive to detect the changes, in particular the martensitic transformation, in samples annealed above 850 degrees C (austenitic regime). (C) 2010 Elsevier B.V. All rights reserved.

Heat treatment influence on the superconducting properties of nanometric-scale Nb(3)Sn wires with Cu-Sn artificial pinning centers

Since the discovery of Nb(3)Sn superconductors many efforts have been expended to improve the transport properties in these materials. In this work, the heat treatment profiles for Nb(3)Sn superconductor wires with Cu(Sn) artificial pinning centers (APCs) with nanometric-scale sizes were analyzed in an attempt to improve the critical current densities and upper critical magnetic field. The methodology to optimize the heat treatment profiles in respect to the diffusion, reaction and formation of the superconducting phases is described. Microstructural characterization, transport and magnetic measurements were performed in an attempt to relate the microstructure to the pinning mechanisms acting in the samples. It was concluded that the maximum current densities occur due to normal phases (APCs) that act as the main pinning centers in the global behavior of the Nb(3)Sn superconducting wire. The APC technique was shown to be very powerful because it permitted mixing of the pinning mechanism. This achievement was not possible in other studies in Nb(3)Sn wires reported up to now.

Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation

Two multinuclear complexes [Fe-6(mu(3)-O)(2)(mu(4)-O-2)L-10(OAc)(2)(H2O)(2)]center dot 2.625Et(2)O center dot 2.375H(2)O (1) and [(Fe11Cl)-Cl-III-(mu(4)-O)(3)(mu(3)-O)(5)L-16(dmf)(2.5)(H2O)(0.5)]center dot Et2O center dot 1.25dmf center dot 3.8H(2)O (2), where HL = 3,4,5-trimethoxybenzoic acid and dmf = dimethylformamide, have been prepared from trinuclear iron(III) carboxylates via their structural rearrangement in dimethylformamide or diethyl ether-dimethylformamide 9:1, respectively, and slow vapor diffusion of diethyl ether into the reaction mixture. Both compounds have been characterized by X-ray diffraction, optical, Mossbauer spectroscopy, and magnetic measurements. Complex 1 possesses a hexanuclear ferric peroxido-dioxido {Fe-6(O-2)(O)(2)}(12+) core unit, which adopts a recliner conformation, while complex 2 contains an unprecedented {Fe11O8Cl}(16+) core, in which 9 ferric ions are six-coordinate and the remaining two are five-coordinate. Another structural feature of note of the undecanuclear core is the presence of a deformed cubane entity {Fe-4(mu(3)-O)(mu(4)-O)(3)}(4+). Both complexes act as catalyst precursors for the oxidation of cyclohexane to cyclohexanol and cyclohexanone with aqueous H2O2, in the presence of pyrazinecarboxylic acid. Remarkable TONs and TOFs (the latter mainly for 1) with concomitant quite good yields have been achieved under mild conditions. Moreover, 1 exhibits remarkably high activity in an exceptionally short reaction time (45 min), being unprecedented for any metal catalyzed alkane oxidation by H2O2. The catalytic reactions proceed via Fenton type chemistry.

Mu-Chlorido-Bridged Dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.