Plasma control of morpho-dimensional selectivity of hematite nanostructures

Highly controllablefabrication of the nanowire, nanocone, and mixed nanowire/nanowall arrays of iron oxide (hematite, α-Fe2O3) nanostructures in a simple, environment-friendly process is achieved by exposing the metal foils to low-temperature oxygen plasmas. Very dense forests of thin (≈50 nm) and long (up to several μm) nanowires are grown on the electrically biased substrates, whereas the use of the electrically insulated substrate resulted in the formation of a mixed array of nanowires and nanowalls. The proposed mechanism of the nanostructure growth is supported by the numerical simulations demonstrating the key role of the plasma environment in the growth morphology selection.

Toward a model for predicting magnetic susceptibility of bedrock regolith and soils

One of the Department of Defense's most pressing environmental problems is the efficient detection and identification of unexploded ordnance (UXO). In regions of highly magnetic soils, magnetic and electromagnetic sensors often detect anomalies that are of geologic origin, adding significantly to remediation costs. In order to develop predictive models for magnetic susceptibility, it is crucial to understand modes of formation and the spatial distribution of different iron oxides. Most rock types contain iron and their magnetic susceptibility is determined by the amount and form of iron oxides present. When rocks weather, the amount and form of the oxides change, producing concomitant changes in magnetic susceptibility. The type of iron oxide found in the weathered rock or regolith is a function of the duration and intensity of weathering, as well as the original content of iron in the parent material. The rate of weathering is controlled by rainfall and temperature; thus knowing the climate zone, the amount of iron in the lithology and the age of the surface will help predict the amount and forms of iron oxide. We have compiled analyses of the types, amounts, and magnetic properties of iron oxides from soils over a wide climate range, from semi arid grasslands, to temperate regions, and tropical forests. We find there is a predictable range of iron oxide type and magnetic susceptibility according to the climate zone, the age of the soil and the amount of iron in the unweathered regolith.

Characteristics and alteration origins of matrix minerals in volcaniclastic kimberlite of the Muskox pipe (Nunavut, Canada)

The matrix of volcaniclastic kimberlite (VK) from the Muskox pipe (Northern Slave Province, Nunavut, Canada) is interpreted to represent an overprint of an original clastic matrix. Muskox VK is subdivided into three different matrix mineral assemblages that reflect differences in the proportions of original primary matrix constituents, temperature of formation and nature of the altering fluids. Using whole rock X-ray fluorescence (XRF), whole rock X-ray diffraction (XRD), microprobe analyses, back-scatter electron (BSE) imaging, petrography and core logging, we find that most matrix minerals (serpentine, phlogopite, chlorite, saponite, monticellite, Fe-Ti oxides and calcite) lack either primary igneous or primary clastic textures. The mineralogy and textures are most consistent with formation through alteration overprinting of an original clastic matrix that form by retrograde reactions as the deposit cools, or, in the case of calcite, by precipitation from Ca-bearing fluids into a secondary porosity. The first mineral assemblage consists largely of serpentine, phlogopite, calcite, Fe-Ti oxides and monticellite and occurs in VK with relatively fresh framework clasts. Alteration reactions, driven by deuteric fluids derived from the juvenile constituents, promote the crystallisation of minerals that indicate relatively high temperatures of formation (> 400 °C). Lower-temperature minerals are not present because permeability was occluded before the deposit cooled to low temperatures, thus shielding the facies from further interaction with fluids. The other two matrix mineral assemblages consist largely of serpentine, phlogopite, calcite, +/- diopside, and +/- chlorite. They form in VK that contains more country rock, which may have caused the deposit to be cooler upon emplacement. Most framework components are completely altered, suggesting that larger volumes of fluids drove the alteration reactions. These fluids were likely of meteoric provenance and became heated by the volcaniclastic debris when they percolated into the VK infill. Most alteration reactions ceased at temperatures > 200 °C, as indicated by the absence or paucity of lower-temperature phases in most samples, such as saponite. Recognition that Muskox VK contains an original clastic matrix is a necessary first step for evaluating the textural configuration, which is important for reconstructing the physical processes responsible for the formation of the deposit.

Reduction in arterial wall strain with aggressive lipid-lowering therapy in patients with carotid artery disease

Background: Inflammation and biomechanical factors have been associated with the development of vulnerable atherosclerotic plaques. Lipid-lowering therapy has been shown to be effective in stabilizing them by reducing plaque inflammation. Its effect on arterial wall strain, however, remains unknown. The aim of the present study was to investigate the role of high- and low-dose lipid-lowering therapy using an HMG-CoA reductase inhibitor, atorvastatin, on arterial wall strain. Methods and Results: Forty patients with carotid stenosis >40% were successfully followed up during the Atorvastatin Therapy: Effects on Reduction Of Macrophage Activity (ATHEROMA; ISRCTN64894118) Trial. All patients had plaque inflammation as shown by intraplaque accumulation of ultrasmall super paramagnetic particles of iron oxide on magnetic resonance imaging at baseline. Structural analysis was performed and change of strain was compared between high- and low-dose statin at 0 and 12 weeks. There was no significant difference in strain between the 2 groups at baseline (P=0.6). At 12 weeks, the maximum strain was significantly lower in the 80-mg group than in the 10-mg group (0.085±0.033 vs. 0.169±0.084; P=0.001). A significant reduction (26%) of maximum strain was observed in the 80-mg group at 12 weeks (0.018±0.02; P=0.01). Conclusions: Aggressive lipid-lowering therapy is associated with a significant reduction in arterial wall strain. The reduction in biomechanical strain may be associated with reductions in plaque inflammatory burden.

Temporal dependence of in vivo USPIO-enhanced MRI signal changes in human carotid atheromatous plaques

Introduction: Ultrasmall superparamagnetic iron oxide (USPIO)-enhanced MRI has been shown to be a useful modality to image activated macrophages in vivo, which are principally responsible for plaque inflammation. This study determined the optimum imaging time-window to detect maximal signal change post-USPIO infusion using T1-weighted (T1w), T2*- weighted (T2*w) and quantitative T2*(qT 2*) imaging. Methods: Six patients with an asymptomatic carotid stenosis underwent high resolution T1w, T2*w and qT2*MR imaging of their carotid arteries at 1.5 T. Imaging was performed before and at 24, 36, 48, 72 and 96 h after USPIO (Sinerem™, Guerbet, France) infusion. Each slice showing atherosclerotic plaque was manually segmented into quadrants and signal changes in each quadrant were fitted to an exponential power function to model the optimum time for post-infusion imaging. Results: The power function determining the mean time to convergence for all patients was 46, 41 and 39 h for the T1w, T 2*w and qT2*sequences, respectively. When modelling each patient individually, 90% of the maximum signal intensity change was observed at 36 h for three, four and six patients on T1w, T 2*w and qT2*, respectively. The rates of signal change decrease after this period but signal change was still evident up to 96 h. Conclusion: This study showed that a suitable imaging window for T 1w, T2*w and qT2*signal changes post-USPIO infusion was between 36 and 48 h. Logistically, this would be convenient in bringing patients back for one post-contrast MRI, but validation is required in a larger cohort of patients.

Utility of USPIO-enhanced MR imaging to identify inflammation and the fibrous cap: A comparison of symptomatic and asymptomatic individuals

Background and purpose: Inflammation is a risk factor the vulnerable atheromatous plaque. This can be detected in vivo on high-resolution magnetic resonance (MR) imaging using a contrast agent, Sinerem™, an ultra-small super-paramagnetic iron oxide (USPIO). The aim of this study was to explore whether there is a difference in the degree of MR defined inflammation using USPIO particles, between symptomatic and asymptomatic carotid plaques. We report further on its T1 effect of enhancing the fibrous cap, which may allow dual contrast resolution of carotid atheroma. Methods: Twenty patients with carotid stenosis (10 symptomatic and 10 asymptomatic) underwent multi-sequence MR imaging before and 36 h post-USPIO infusion. Images were manually segmented into quadrants and signal change in each quadrant was calculated following USPIO administration. Mean signal change across all quadrants were compared between the two groups. Results: Symptomatic patients had significantly more quadrants with a signal drop than asymptomatic individuals (75% vs. 32%, p < 0.01). Asymptomatic plaques had more quadrants with signal enhancement than symptomatic ones (68% vs. 25%, p < 0.05); their mean signal change was also higher (46% vs. 15%, p < 0.01) and this appeared to correlate with a thicker fibrous cap on histology. Conclusions: Symptomatic patients had more quadrants with signal drop suggesting larger inflammatory infiltrates. Asymptomatic individuals showed significantly more enhancement possibly suggesting greater stability as a result of thicker fibrous caps. However, some asymptomatic plaques also had focal areas of signal drop, suggesting an occult macrophage burden. If validated by larger studies, USPIO may be a useful dual contrast agent able to improve risk stratification of patients with carotid stenosis and inform selection for intervention.

Correlation of carotid atheromatous plaque inflammation using USPIO-enhanced MR imaging with degree of luminal Stenosis

BACKGROUND AND PURPOSE Inflammation is a recognized risk factor for the vulnerable atherosclerotic plaque. The study explores the relationship between the degree of Magnetic Resonance (MR)"defined inflammation using Ultra Small Super-Paramagnetic Iron Oxide (USPIO) particles and the severity of luminal stenosis in asymptomatic carotid plaques. METHODS Seventy-one patients with an asymptomatic carotid stenosis of ĝ‰¥40% underwent multi-sequence USPIO-enhanced MR imaging. Stenosis severity was measured according to the NASCET and ECST methods. RESULTS No demonstrable relationship between inflammation as measured by USPIO-enhanced signal change and the degree of luminal stenosis was found. CONCLUSIONS Inflammation and stenosis are likely to be independent risk factors, although this needs to be further validated.

Correlation of carotid atheromatous plaque inflammation with biomechanical stress: Utility of USPIO enhanced MR imaging and finite element analysis

Objective: The aim of this study was to explore whether there is a relationship between the degree of MR-defined inflammation using ultra small super-paramagnetic iron oxide (USPIO) particles, and biomechanical stress using finite element analysis (FEA) techniques, in carotid atheromatous plaques. Methods and Results: 18 patients with angiographically proven carotid stenoses underwent multi-sequence MR imaging before and 36 h after USPIO infusion. T2 * weighted images were manually segmented into quadrants and the signal change in each quadrant normalised to adjacent muscle was calculated after USPIO administration. Plaque geometry was obtained from the rest of the multi-sequence dataset and used within a FEA model to predict maximal stress concentration within each slice. Subsequently, a new statistical model was developed to explicitly investigate the form of the relationship between biomechanical stress and signal change. The Spearman's rank correlation coefficient for USPIO enhanced signal change and maximal biomechanical stress was -0.60 (p = 0.009). Conclusions: There is an association between biomechanical stress and USPIO enhanced MR-defined inflammation within carotid atheroma, both known risk factors for plaque vulnerability. This underlines the complex interaction between physiological processes and biomechanical mechanisms in the development of carotid atheroma. However, this is preliminary data that will need validation in a larger cohort of patients.

Simple synthesis and spectroscopic studies on cobalt added ZnO nanocrystals

Cobalt doped zinc oxide nanoparticles were prepared through simple wet chemical method. X-ray diffraction studies confirm the prepared particles are in wurtzite structure. Scanning Electron Microscopy studies show the shape and morphology of the particles. To identify the presence of cobalt in ZnO, Energy Dispersive X-ray analysis was done. Optical absorption measurements show the presence of exciton peak at 375 nm. Photoluminescence studies were done with the excitation wavelength of 330 nm, which shows the emission because of exciton recombination and oxygen vacancy.

Characterisation of cellulose- and lignin-based materials using x-ray scattering methods

Wood is an important material for the construction and pulping industries. Using x-ray diffraction the microfibril angle of Sitka spruce wood was studied in the first part of this thesis. Sitka spruce (Picea sitchensis [Bong.] Carr.) is native to the west coast of North America, but due to its fast growth rate, it has also been imported to Europe. So far, its nanometre scale properties have not been systematically characterised. In this thesis the microfibril angle of Sitka spruce was shown to depend significantly on the origin of the tree in the first annual rings near the pith. Wood can be further processed to separate lignin from cellulose and hemicelluloses. Solid cellulose can act as a reducer for metal ions and it is also a porous support for nanoparticles. By chemically reducing nickel or copper in the solid cellulose support it is possible to get small nanoparticles on the surfaces of the cellulose fibres. Cellulose supported metal nanoparticles can potentially be used as environmentally friendly catalysts in organic chemistry reactions. In this thesis the size of the nickel and copper containing nanoparticles were studied using anomalous small-angle x-ray scattering and wide-angle x-ray scattering. The anomalous small-angle x-ray scattering experiments showed that the crystallite size of the copper oxide nanoparticles was the same as the size of the nanoparticles, so the nanoparticles were single crystals. The nickel containing nanoparticles were amorphous, but crystallised upon heating. The size of the nanoparticles was observed to be smaller when the reduction of nickel was done in aqueous ammonium hydrate medium compared to reduction made in aqueous solution. Lignin is typically seen as the side-product of wood industries. Lignin is the second most abundant natural polymer on Earth, and it possesses potential to be a useful material for many purposes in addition to being an energy source for the pulp mills. In this thesis, the morphology of several lignins, which were produced by different separation methods from wood, was studied using small-angle and ultra small-angle x-ray scattering. It was shown that the fractal model previously proposed for the lignin structure does not apply to most of the extracted lignin types. The only lignin to which the fractal model could be applied was kraft lignin. In aqueous solutions the average shape of the low molar mass kraft lignin particles was observed to be elongated and flat. The average shape does not necessarily correspond to the shape of the individual particles because of the polydispersity of the fraction and due to selfassociation of the particles. Lignins, and especially lignosulfonate, have many uses as dispersants, binders and emulsion stabilisers. In this thesis work the selfassociation of low molar mass lignosulfonate macromolecules was observed using small-angle x-ray scattering. By taking into account the polydispersity of the studied lignosulfonate fraction, the shape of the lignosulfonate particles was determined to be flat by fitting an oblate ellipsoidal model to the scattering intensity.

Collapse Behavior of an Artificially Cemented Clayey Silt

The present study examines the role of interparticle cementation in the collapse behavior of two partly saturated (S-r = 4 to 12%) and very highly porous (initial void ratio = 1.5 to 2) laboratory-desiccated clayey silt specimens containing varying amounts (5 and 15% by dry weight of the respective specimens) of the cementitious iron oxides hematite and goethite, which are generally encountered in tropical residual soils. Kaolinite is the representative clay mineral of the soil matrix used for this research. Interparticle cementation by the crystalline iron oxides was generated in the laboratory by repeated (six times) wetting and drying of the iron-hydroxide-admixed clayey silt specimens under ambient conditions of temperature and humidity. Results showed that, for a given laboratory-desiccated clayey silt specimen (i.e., a specimen containing 5 or 15% of iron oxide on a dry weight basis), the amount of collapse (represented by Delta epsilon, the change in vertical strain upon wetting under constant pressure) increases with an increase in the experimental loading under which the specimen is inundated. The laboratory results also show that the desiccated specimen with a higher iron oxide content (containing 15% iron oxide by dry weight of the desiccated specimen) in spite of a lower dry unit weight (gamma(d) = 8.8 kN/m(3)) undergoes a lesser amount of collapse on soaking under a constant external stress (50 or 100 kPa) than the desiccated specimen with a lower iron oxide content (i.e., containing 5% iron oxide by dry weight of the desiccated specimen, gamma(d) = 10.4 KN/m(3)). Based on the X-ray diffraction results and the stress-strain relationships obtained from isotropically consolidated undrained triaxial tests, it is suggested that the laboratory-desiccated specimens are characterized by a metastable bonding provided by capillary suction and the crystalline iron oxides. On soaking under load owing to the loss of the metastable bonding, collapse of the laboratory-desiccated specimens occurs. Also, in the case of the laboratory-desiccated specimen with a higher iron oxide content, the presence of a stronger interparticle cementation (due to a greater abundance of crystalline iron oxides) and a higher initial moisture content are considered responsible for the specimen exhibiting a lower amount of collapse in comparison to that exhibited by the desiccated specimen with a lesser iron oxide content.

Reduction of electric are furnace slags in stainless steelmaking - Part 1 Observations

Simultaneous reduction of iron and chromium oxides from synthetic electric are furnace stainless steelmaking slag in a graphite crucible has been studied. Above the melting point of iron the reduction of iron oxide leads to a carbon saturated Fe-C melt, but below the melting point of iron initially solid iron or iron carbide forms on the crucible surface. Only when a certain number of Fe-C droplets are formed does the reduction of chromium oxide start to form an Fe-Cr-C alloy. The reaction proceeds with pronounced foaming which depends on the basicity, temperature, and iron oxide content of the slag. IS/1352a (C) 1998 The Institute of Materials.

Electrochemical aspects of leaching of ocean nodules in the presence and absence of microorganisms

instead of using chemical-reducing agents to facilitate the reduction and dissolution of manganese and iron oxide in the ocean nodule, electrochemical reduction based on two approaches, namely, cathodic polarization and galvanic interaction, can also be considered as attractive alternatives. Galvanic leaching of ocean nodules in the presence of pyrite and pyrolusite for complete recovery of Cu, Ni and Co has been discussed. The key for successful and efficient dissolution of copper, nickel and cobalt from ocean nodules depends on prior reduction of the manganese and ferric oxides with which the above valuable nonferrous metals are interlocked. Polarization studies using a slurry electrode system indicated that maximum dissolution of iron and manganese due to electrochemical reduction occurred at negative DC potentials of -600 mV (SCE) and -1400 mV (SCE). The present work is also relevant to galvanic bioleaching of ocean nodules using autotrophic microorganisms, such as Thiobacillus ferrooxidans and T thiooxidans, which resulted in significant dissolution of copper, nickel and cobalt at the expense of microbiologically generated acids. Various electrochemical and biochemical mechanisms are outlined and the electroleaching and galvanic processes so developed are shown to yield almost complete dissolution of all metal values. (C) 2002 Elsevier Science B.V. All rights reserved.

Development of uniformly grown ZnO NPs films using single precursor solution by pulsed spray pyrolysis technique

In this article, we have reported the controlled synthesis of uniformly grown zinc oxide nanoparticles (ZnO NPs) films by a simple, low-cost, and scalable pulsed spray pyrolysis technique. From the surface analysis it is noticed that the as-deposited films have uniformly dispersed NPs-like morphology. The structural studies reveal that these NPs films have highly crystalline hexagonal crystal structure, which are preferentially orientated along the (001) planes. The size of the NPs varied between 5 and 100 nm, and exhibited good stoichiometric chemical composition. Raman spectroscopic analysis reveals that these ZnO NPs films have pure single phase and hexagonal crystal structure. These unique nanostructured films exhibited a low electrical resistivity (5 Omega cm) and high light transmittance (90 %) in visible region.

Synthesis and characterization of porous flowerlike alpha-Fe2O3 nanostructures for supercapacitor application

Porous flower-like alpha-Fe2O3 nanostructures synthesized by an ethylene glycol mediated self-assembly process are crystalline and porous with BET surface area of 64.6 m(2) g(-1). The discharge capacitance is 127 F g(-1) when the electrodes are cycled in 0.5 M Na2SO3 at a current density of 1 A g(-1). Capacitance retention after 1000 cycles is about 80% of the initial capacitance. The high discharge capacitance and its retention are attributed to high surface area and porosity of the iron oxide. As the iron oxides are inexpensive, the nano alpha-Fe2O3 is expected to be of potential use for supercapacitor application.