The lateritic profile of Balkouin, Burkina Faso: geochemistry, mineralogy and genesis

This study reports on the geochemical and mineralogical characterization of a lateritic profile cropping out in the Balkouin area, Central Burkina Faso, aimed at obtaining a better understanding of the processes responsible for the formation of the laterite itself and the constraints to its development. The lateritic profile rests on a Paleoproterozoic basement mostly composed of granodioritic rocks related to the Eburnean magmatic cycle passing upwards to saprolite and consists of four main composite horizons (bottom to top): kaolinite and clay-rich horizons, mottled laterite and iron-rich duricrust. In order to achieve such a goal, a multi-disciplinary analytical approach was adopted, which includes inductively coupled plasma (ICP) atomic emission and mass spectrometries (ICP-AES and ICP-MS respectively), X-ray powder diffraction (XRPD), scanning electron microscopy with energy dispersive spectrometry (SEM-EDS) and micro-Raman spectroscopy.

The geochemical data, and particularly the immobile elements distribution and REE patterns, show that the Balkouin laterite is the product of an in situ lateritization process that involved a strong depletion of the more soluble elements (K, Mg, Ca, Na, Rb, Sr and Ba) and an enrichment in Fe; Si was also removed, particularly in the uppermost horizons. All along the profile the change in composition is coupled with important changes in mineralogy. In particular, the saprolite is characterized by occurrence of abundant albitic plagioclase, quartz and nontronite; kaolinite is apparently absent. The transition to the overlying lateritic profile marks the breakdown of plagioclase and nontronite, thus allowing kaolinite to become one of the major components upwards, together with goethite and quartz. The upper part of the profile is strongly enriched in hematite (+ kaolinite). Ti oxides (at least in part as anatase) and apatite are typical accessory phases, while free aluminum hydroxides are notably absent. Mass change calculations emphasize the extent of the mass loss, which exceeds 50 wt% (and often 70 wt%) for almost all horizons; only Fe was significantly concentrated in the residual system.

The geochemical and mineralogical features suggest that the lateritic profile is the product of a continuous process that gradually developed from the bedrock upwards, in agreement with the Schellmann classic genetic model. The laterite formation must have occurred at low pH (? 4.5) and high Eh (? 0.4) values, i.e., under acidic and oxidizing environments, which allowed strongly selective leaching conditions. The lack of gibbsite and bohemite is in agreement with the compositional data: the occurrence of quartz (± amorphous silica) all along the profile was an inhibiting factor for the formation of free aluminum hydroxides.

Room-temperature single phase multiferroic magnetoelectrics: Pb(Fe,M)x(Zr,Ti)(1−x)O3 [M=Ta, Nb]

We describe extensive studies on a family of perovskite oxides that are ferroelectric and ferromagnetic at ambient temperatures. The data include x-ray diffraction, Raman spectroscopy, measurements of ferroelectric and magnetic hysteresis, dielectric constants, Curie temperatures, electron microscopy
(both scanning electron microscope and transmission electron microscopy (TEM)) studies, and both longitudinal and transverse magnetoelectric constants a33 and a31. The study extends earlier work to lower Fe, Ta, and Nb concentrations at the B-site (from 15%–20% down to 5%). The magnetoelectric
constants increase supralinearly with Fe concentrations, supporting the earlier conclusions of a key role for Fe spin clustering. The room-temperature orthorhombic C2v point group symmetry inferred from earlier x-ray diffraction studies is confirmed via TEM, and the primitive unit cell size is found to be the basic perovskite Z¼1 structure of BaTiO3, also the sequence of phase transitions with increasing temperature from rhombohedral to orthorhombic to tetragonal to cubic mimics barium titanate.

Steam reforming of ethanol over Co3O4–Fe2O3 mixed oxides

Co3O4, Fe2O3 and a mixture of the two oxides Co–Fe (molar ratio of Co3O4/Fe2O3 = 0.67 and atomic ratio of Co/Fe = 1) were prepared by the calcination of cobalt oxalate and/or iron oxalate salts at 500 °C for 2 h in static air using water as a solvent/dispersing agent. The catalysts were studied in the steam reforming of ethanol to investigate the effect of the partial substitution of Co3O4 with Fe2O3 on the catalytic behaviour. The reforming activity over Fe2O3, while initially high, underwent fast deactivation. In comparison, over the Co–Fe catalyst both the H2 yield and stability were higher than that found over the pure Co3O4 or Fe2O3 catalysts. DRIFTS-MS studies under the reaction feed highlighted that the Co–Fe catalyst had increased amounts of adsorbed OH/water; similar to Fe2O3. Increasing the amount of reactive species (water/OH species) adsorbed on the Co–Fe catalyst surface is proposed to facilitate the steam reforming reaction rather than decomposition reactions reducing by-product formation and providing a higher H2 yield.

Switching ferroelectric domain configurations using both electric and magnetic fields in Pb(Zr,Ti)O3–Pb(Fe,Ta)O3 single-crystal lamellae

Thin single-crystal lamellae cut from Pb(Zr,Ti)O3–Pb(Fe,Ta)O3 ceramic samples have been integrated into simple coplanar capacitor devices. The influence of applied electric and magnetic fields on ferroelectric domain configurations has been mapped, using piezoresponse force microscopy. The extent to which magnetic fields alter the ferroelectric domains was found to be strongly history dependent: after switching had been induced by applying electric fields, the susceptibility of the domains to change under a magnetic field (the effective magnetoelectric coupling parameter) was large. Such large, magnetic field-induced changes resulted in a remanent domain state very similar to the remanent state induced by an electric field. Subsequent magnetic field reversal induced more modest ferroelectric switching.

Studies of the Room-Temperature Multiferroic Pb(Fe0.5Ta0.5)0.4(Zr0.53Ti0.47)0.6O3: Resonant Ultrasound Spectroscopy, Dielectric, and Magnetic Phenomena

Recently, lead iron tantalate/lead zirconium titanate (PZTFT) was demonstrated to possess large, but unreliable, magnetoelectric coupling at room temperature. Such large coupling would be desirable for device applications but reproducibility would also be critical. To better understand the coupling, the properties of all 3 ferroic order parameters, elastic, electric, and magnetic, believed to be present in the material across a range of temperatures, are investigated. In high temperature elastic data, an anomaly is observed at the orthorhombic mm2 to tetragonal 4mm transition, Tot = 475 K, and a softening trend is observed as the temperature is increased toward 1300 K, where the material is known to become cubic. Thermal degradation makes it impos- sible to measure elastic behavior up to this temperature, however. In the low temperature region, there are elastic anomalies near ≈40 K and in the range 160–245 K. The former is interpreted as being due to a magnetic ordering transition and the latter is interpreted as a hysteretic regime of mixed rhom- bohedral and orthorhombic structures. Electrical and magnetic data collected below room temperature show anomalies at remarkably similar temperature ranges to the elastic data. These observations are used to suggest that the three order parameters in PZTFT are strongly coupled.

Adsorption Study using Optimised 3D Organised Mesoporous Silica Coated with Fe and Al Oxides for Specific As(III) and As(V) Removal from Contaminated Synthetic Groundwater

This work presents the possibility of optimising 3D Organised Mesoporous Silica (OMS) coated with both iron and aluminium oxides for the optimal removal of As(III) and As(V) from synthetic contaminated water. The materials developed were fully characterised and were tested for removing arsenic in batch experiments. The effect of total Al to Fe oxides coating on the selective removal of As(III) and As(V) was studied. It was shown that 8% metal coating was the optimal configuration for the coated OMS materials in removing arsenic. The effect of arsenic initial concentration and pH, kinetics and diffusion mechanisms was studied, modelled and discussed. It was shown that the advantage of an organised material over an un-structured sorbent was very limited in terms of kinetic and diffusion under the experimental conditions. It was shown that physisorption was the main adsorption process involved in As removal by the coated OMS. Maximum adsorption capacity of 55 mg As(V).g-1 was noticed at pH 5 for material coated with 8% Al oxides while 35 mg As(V).g-1 was removed at pH 4 for equivalent material coated with Fe oxides.

Electron-impact excitation of the astrophysically important singly ionized Fe-peak ions Sc and Ti

In this work we report on the evaluation of electron-impact collision strengths and Maxwellian averaged effective collision strengths for the lowly-ionized Fe-peak elements Sc II and Ti II using the parallel R-matrix package RMATRX II.

The Nature of Magnetoelectric Coupling in Pb(Zr,Ti)O3-Pb(Fe,Ta)O3

The coupling between magnetization and polarization in a room temperature multiferroic (Pb(Zr,Ti)O3–Pb(Fe,Ta)O3) is explored by monitoring changes in capacitance that occur when a magnetic field is applied in each of three orthogonal directions. Magnetocapacitance effects, consistent with P2M2 coupling, are strongest when fields are applied in the plane of the single crystal sheet investigated.

Evaluation of strontium-site-deficient Sr2Fe1.4Co0.1Mo0.5O6-δ-based perovskite oxides as intermediate temperature solid oxide fuel cell cathodes

In this paper strontium-site-deficient Sr₂Fe_1.4Co_0.1Mo_0.5O_6-δ-based perovskite oxides (S_xFCM) were prepared and evaluated as the cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). All samples exhibited a cubic phase structure and the lattice shrinked with increasing the Sr-deficiency as shown in XRD patterns. XPS results determined that the transition elements (Co/Fe/Mo) in S_xFCM oxides were in a mixed valence state, demonstrating the small polaron hopping conductivity mechanism existed. Among the samples, S_1.950FCM presented the lowest coefficient of thermal expansion of 15.62 × 10^-6 K^-1, the highest conductivity value of 28 S cm^-1 at 500 °C, and the lowest interfacial polarization resistance of 0.093 Ω cm² at 800 °C, respectively. Furthermore, an anode-supported single cell with a S_1.950FCM cathode was prepared, demonstrating a maximum power density of 1.16 W cm^-2 at 800 °C by using wet H₂ (3% H₂O) as the fuel and ambient air as the oxidant. These results indicate that the introduction of Sr-deficiency can dramatically improve the electrochemical performance of Sr₂Fe_1.4Co_0.1Mo_0.5O_6-δ, showing great promise as a novel cathode candidate material for IT-SOFCs.

Catalytic Role of Metal Oxides in Gold-Based Catalysts: A First Principles Study of CO Oxidation on TiO2 Supported Au

CO oxidation on TiO2 supported Au has been studied using density functional theory calculations. Important catalytic roles of the oxide have been identified: (i) CO oxidation occurs at the interface between Au and the oxide with a very small barrier; and (ii) O-2 adsorption at the interface is the key step in the reaction. The physical origin of the oxide promotion effect has been further investigated: The oxide enhances electron transfer from the Au to the antibonding states of O-2, giving rise to (i) strong ionic bonding between the adsorbed O-2, Au, and the Ti cation; and (ii) a significant activation of O-2 towards CO oxidation.

Synthesis and NMR Characterization of Titanium and Zirconium Oxides Incorporated in SBA-15

Single oxides of Ti and Zr incorporated SBA-15 were prepared and characterized by N-2 adsorption, NMR, and XPS techniques. Si-29 MAS NMR results suggest the formation of Si-O-X linkages (X: Ti or Zr) by an increase in the ratio of Q(3)/Q(4) in the presence of Ti or Zr. XPS analysis of Ti-SBA-15 catalysts indicate the presence of Ti-O-Si bonds in addition to Ti-O-Ti and Si-O-Si bonds, supporting the NMR evidence.

Oxidative dehydrogenation of propane with N2O over Fe-ZSM-5 and Fe-SiO2: Influence of the iron species and acid sites

A series of iron containing zeolites with varying Si/Al ratios (11.5-140) and low iron content (similar to 0.9 wt.% Fe) have been synthesised by solid-state ion exchange with commercially available zeolites and tested, for the first time, in the oxidative dehydrogenation of propane (ODHP) with N2O. The samples were characterised by XRD, N-2-Adsorption, NH3-TPD and DR-UV-vis spectroscopy. The acidity of the Fe-ZSM-5 can be controlled by high temperature and steam treatments and Si/Al ratio. The selectivity and yield of propene were found to be the highest over Fe-ZSM-5 with low Al contents and reduced acidity. The initial propene yield over Fe-ZSM-5 was significantly higher than that of Fe-SiO2 since the presence of weak and/or medium acid sites together with oligonuclear iron species and iron oxides on the ZSM-5 are found to enhance the N2O activation. The coking of Fe-ZSM-5 catalysts could also be controlled by reduction of the surface acidity of ZSM-5 and by the use of O-2 in addition to N2O as the oxidant. Fe-ZSM-5 zeolites prepared with solid-state method have been shown to have comparable activity and better stability towards coking compared with Fe-ZSM-5 zeolites prepared by liquid ion exchange and hydrothermal synthesis methods. (C) 2012 Elsevier B.V. All rights reserved.

Heterogeneous oxidation of pyrimidine and alkyl thioethers in ionic liquids over mesoporous Ti or Ti/Ge catalysts

Heterogeneous catalytic oxidation of a series of thioethers (2-thiomethylpyrimidine, 2-thiomethyl-4,6-dimethyl-pyrimidine, 2-thiobenzylpyrimidine, 2-thiobenzyl-4,6-dimethylpyrimidine, thioanisole, and n-heptyl methyl sulfide) was performed in ionic liquids by using MCM-41 and UVM-type mesoporous catalysts containing Ti, or Ti and Ge. A range of triflate, tetrafluoroborate, trifluoroacetate, lactate and bis(trifluoromethanesulfonyl)imide-based ionic liquids were used. The oxidations were carried out by using anhydrous hydrogen peroxide or the urea-hydrogen peroxide adduct and showed that ionic liquids are very effective solvents, achieving greater reactivity and selectivity than reactions performed in dioxane. The effects of halide and acid impurities on the reactions were also investigated. Recycling experiments on catalysts were carried out in order to evaluate Ti leaching and its effect on activity and selectivity.

3D FEM simulation of helical milling hole process for titanium alloy Ti-6Al-4V

As an emerging hole-machining methodology, helical milling process has become increasingly popular in aeromaterials manufacturing research, especially in areas of aircraft structural parts, dies, and molds manufacturing. Helical milling process is highly demanding due to its complex tool geometry and the progressive material failure on the workpiece. This paper outlines the development of a 3D finite element model for helical milling hole of titanium alloy Ti-6Al-4V using commercial FE code ABAQUS/Explicit. The proposed model simulates the helical milling hole process by taking into account the damage initiation and evolution in the workpiece material. A contact model at the interface between end-mill bit and workpiece has been established and the process parameters specified. Furthermore, a simulation procedure is proposed to simulate different cutting processes with the same failure parameters. With this finite element model, a series of FEAs for machined titanium alloy have been carried out and results compared with laboratory experimental data. The effects of machining parameters on helical milling have been elucidated, and the capability and advantage of FE simulation on helical milling process have been well presented.