The effect of vacuum annealing on the remediation abilities of iron and iron−nickel nanoparticles

Zero-valent iron nanoparticles are effective remediators of uranium from solution. It is postulated that the improved core crystallinity and the migration of impurity phases to the nanoparticle surfaces induced by annealing may improve their corrosion resistance and reactive lifespan. The ability of annealed and non-annealed Fe and FeNi nanoparticles to remediate a U-contaminated effluent from AWE, Aldermaston was investigated. Nanoparticles (of diameter typically between 0 and 100 nm) were introduced to the effluent and allowed to react for 7 days during which the liquid and nanoparticulate solids were periodically sampled. In all the systems, the maximum U-uptake occurred within 1 h of introduction, with variable efficiency. The Fe nanoparticles removed 98% of the total U from solution, resulting in a final U-concentration of <4 μg/L. A rapid release of Fe into solution was recorded early in the reaction period: attributed to limited partial dissolution of the nanoparticles. Annealing the Fe nanoparticles did not affect their efficiency but the dissolution of Fe was significantly reduced and X-ray Photoelectron Spectroscopy indicated slower progressive oxidation. The performance of the FeNi nanoparticles was significantly improved by annealing, with U-uptake increasing from 50 to 94%. Although the dissolution of Ni was completely inhibited by annealing, the Fe dissolution increased compared to that observed for the non-annealed FeNi nanoparticles, in contrast to behaviour exhibited by Fe-annealed nanoparticles. In all the systems, U was reduced to U(IV) and retained on the surfaces of the nanoparticulate solids for up to 48 h; the U-stability was not affected by annealing the Fe or the FeNi nanoparticles before use.     

Does iron inhibit cryptoendolithic microbial communities?

Photosynthetic activity of three cryptoendolithic microbial communities was studied under controlled conditions in the laboratory. In two of these communities, the dominant organisms were lichens, collected from Linnaeus Terrace and from Battleship Promontory. The third community, dominated by cyanobacteria, was collected from Battleship Promontory. Both sites are in the ice-free valleys of southern Victoria Land. Previous efforts have shown how physical conditions can influence metabolic activity in endolithic communities (Kappen and Friedmann 1983; Kappen, Friedmann, and Garty 1981; Vestal, Federle, and Friedmann 1984). Biological activity can also be strongly influenced by the chemical environment. Inorganic nutrients such as nitrate, ammonia, and phosphate are often limiting factors, so their effects on photosynthetic carbon-14 bicarbonate incorporation were investigated. Iron and manganese are two metals present in Linnaeus Terrace and Battleship Promontory sandstones, and their effects on photosynthesis were also studied. The results may add to our understanding of biogeochemical interactions within this unique microbial community.     

Comparative study of core–shell iron/iron oxide gold covered magnetic nanoparticles obtained in different conditions

In this study, we report the synthesis and characterization of the core–shell Fe covered with Au shells nanoparticles with mean diameters between 5 and 8 nm. The inverse micelles method was utilized to produce the samples. X-ray diffraction studies show that both core–shell systems have the expected crystalline structure. High resolution transmission electron microscopy and atomic emission spectroscopy techniques give additional information concerning the structure and composition of nanoparticles. An intermediate shell of amorphous oxidized iron was found between the magnetic Fe core and the external gold shell. The magnetic behavior of different core–shell samples shows no hysteresis loop indicating the superparamagnetic behavior of Fe@Au systems. The superparamagnetic behavior is also evidenced from FC and ZFC dependences of the magnetization versus temperature. By using the temperature dependence of the thermoremanent magnetization combined with magnetization versus applied magnetic field, the effective anisotropy constant was determined. The Fe/Au interface contribution to the effective anisotropy constant was calculated and discussed in relation with the combined shape and stress anisotropies.     

Mössbauer studies of iron stabilised polymethacrylates

Polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA) and polybutyl methacrylate (PBuMA) containing ferric chloride and ferrous sulphate as stabilisers, were prepared by free radical polymerization. Mössbauer spactra of ferrous sulphate stabilised polymers don't show any change in the value of isomer shift (1.30 mm/s) while quadrupole splitting values are quite different from those for pure ferrous sulphate. This indicates that environment of Fe²⁺ moiety changes in polymers and thus stabilises the polymers. In case of ferric chloride stabilised polymers the isomer shift values don't differ significantly for different polymethacrylates but quadrupole splitting values increase from polymethyl methacrylate to polybutyl methacrylate. The TGA analysis shows that the inclusion of iron salts stabilises the polymers by 40°C (approx.) and at higher temperatures α-Fe₂O₃ is formed.     

Laser initiation of PETN–iron nanoparticle composites

The dependences of the probability of explosion initiation in pentaerythritol tetranitrate samples with different contents of iron nanoparticles on the fluence of the first- (λ = 1064 nm) and second-harmonic (λ = 532 nm) pulses of a neodymium laser are measured. The laser initiation threshold for PETN–iron nanoparticle composites nonmonotonically depends on the mass fraction of nanoparticles. The optimal values of the mass fraction of iron nanoparticles at which the sensitivity to laser irradiation is maximal (0.4 wt % for the first harmonic and 0.15 wt % for the second) are determined. It is demonstrated that the amplitude of the optoacoustic signal under non-explosion conditions reaches its maximum for composites with the optimal values of the mass fraction of nanoparticles.     

Preparation and characterization of iron–molybdate thin films

Mixed Fe–Mo oxides are used in industrial catalytic processes of selective oxidation of methanol to formaldehyde. For better understanding of the structure-reactivity relationships of these catalysts we aim to prepare well-ordered iron–molybdate thin films as model catalysts. Here we have studied Mo deposition onto Fe₃O₄ (111) thin films produced on Pt(111) as a function of Mo coverage and annealing temperature using LEED, AES, STM and IRAS. At low temperatures, the iron oxide film is covered by Mo = O terminated molybdena nanoparticles. Upon oxidation at elevated temperatures (T > 900 K), Mo species migrate into the film and form new bonds with oxygen in the film. The resulting films maintain the crystal structure of Fe₃O₄, and the surface undergoes a (√3 × √3)R30° reconstruction. The structure is rationalized in terms of Fe substitution by Mo in the surface layers.     

Structure and magnetism in compressed iron–cobalt alloys

Combined Co K-edge XANES-XMCD and XRD measurements were used to shed light on the magnetic and structural phase diagram of the Fe_1?x Co _x alloy under HP in the Co-rich region (x≥0.5). At 0.5≤x≤0.75, the alloy shows a pressure-induced structural/magnetic phase transition from bcc-FM to hcp-non-FM phase just like pure iron but at higher pressures. The x=0.9 sample has an fcc structure in the pressure range investigated but presents an FM to non-FM transition at P=64 GPa, a significantly lower pressure compared with pure Co (predicted ≈120 GPa), showing that Fe impurities strongly affect the HP Co response.     

Processing of gadolinium–iron garnet under non-equilibrium conditions

We have investigated the mechanosynthesis of gadolinium iron garnet (GdIG) by high-energy ball-milling of 3.(Gd₂O₃)?+?10.(α-Fe) followed by thermal annealing conducted at moderate temperatures (1100 °C). The samples were characterized by X-ray diffraction and Mössbauer spectroscopy in order to determine the influence of the milling time on the final products. For as-milled samples the results revealed the enlargement of the magnetic component belonging to iron and a discrete paramagnetic component. The formation of a garnet phase was observed in all as-annealed samples treated at 1100 °C for 6 h in quantities proportional to the time of grinding the precursors. Evidently, high-energy ball milling of Gd₂O₃?+?α-Fe powders is an important step in GdIG synthesis by a ceramic method. Single-phase garnet is observed for the samples milled for 12 and 24 h treated at 1100 °C for 6 h.     

Mössbauer spectroscopic properties of tin-doped iron oxides

The ⁵⁷Fe Mössbauer spectra recorded in situ from tin-doped Fe₃O₄ at elevated temperature in vacuo shows the Curie temperature to decrease with increasing concentrations of the dopant. Thermal treatment under oxidising conditions results in the initial formation of tin-doped γ-Fe₂O₃ which subsequently undergoes a phase transformation to tin-doped α-Fe₂O₃. ⁵⁷Fe Mössbauer spectroscopy at elevated temperatures shows the Néel temperature for tin-doped γ-Fe₂O₃ to be lower than that of pure γ-Fe₂O₃. The ¹¹⁹Sn Mössbauer spectra recorded from all the tin-doped iron oxides show the presence of a hyperfine magnetic field at the Sn⁴⁺ site which is more complex in the spectra recorded from tin-doped γ-Fe₂O₃ and α-Fe₂O₃.     

Laser-produced iron nitrides seen by Mössbauer spectroscopy

Mössbauer spectroscopy is a very powerful tool to investigate technological processes performed mainly at the surface of materials. Nitriding of metals and steel is well established in surface engineering, and gas nitriding is used most frequently. Laser nitriding, i.e. the nitrogen take-up from the ambient gas upon irradiation of a steel surface with short laser pulses, is presented in its application to iron, stainless steel and plain carbon steels. It will be demonstrated how Mössbauer spectroscopy in combination with complementary methods (Rutherford backscattering spectroscopy, Resonant nuclear reaction analysis, Nanoindentation) can help to reveal basic mechanisms in these processes.     

Mössbauer study of CO-precipitated Fischer-Tropsch iron catalysts

Mössbauer spectroscopy studies of precipitated Fischer-Tropsch (FT) iron catalysts, viz. 100 Fe/5 Cu/4.2 K/x SiO₂, wherex=0,8, 16, 24, 25, 40, or 100, have shown that reduction of the oxide precursor in CO gives rise to -carbide Fe₅C₂ whose amount decreases with an increase of SiO₂ content. The -carbide is converted into magnetite Fe₃O₄ while catalyzing the FT synthesis reaction. A correlation between FT activity and the content of -carbide in the catalysts was found, which indicated that -carbide is active for FT synthesis reaction.     

Thermal transition behaviour of iron oxide–polypyrrole nanocomposites

Distinct thermal transitions have been observed in nanocomposites based on iron oxide–polypyrrole prepared by simultaneous gelation and polymerization process. The transition behaviour for various iron oxide–polypyrrole compositions was investigated with the help of differential scanning calorimetery. It has been observed that the samples show a magnetic to nonmagnetic transition at 410 °C. The presence of exothermic peak at 410 °C is a strong indication of magnetic transition corresponding to γ-Fe₂O₃ phase of iron oxide to a nonmagnetic α-Fe₂O₃ phase in these nanocomposites. However such a transition was not observed in nanocomposites containing lesser concentration of conducting polymer.     

Grüneisen parameter for HCP iron at extreme compression

The Thomas–Fermi approximation gives the Grüneisen parameter γ=γ_∞=1/2 for all materials at extreme compression (P→∞ or V→0). After re-analyzing the existing experimental data of volume dependence of Grüneisen parameter γ of hexagonal close-packed (HCP) iron, we find that γ=1/2+a(V/V ₀)^1/3+b(V/V ₀) ⁿ , where a, b and n are constants. Based on this new form of γ, the second Grüneisen parameter q, the Debye temperature θ_D and the shear sound velocity v _s of HCP iron are discussed in the present work. It is found that the zero pressure second Grüneisen parameter q ₀=0.654, which is consistent with the previously determined value of HCP iron for Earth's core physics from Dubrovinsky et al. The calculations for the Debye temperature and the shear sound velocity are also found to be in good agreement with the experimental data.     

Mössbauer study of iron removal in a montmorillonite

⁵⁷Fe Mössbauer spectroscopy in conjunction with atomic absorption spectrometry and X-ray powder differaction analyses have been used to study the iron present in a montmorillonite prior to and after different successive stages of two deferration processes. Fe³⁺ ions occupy mainly octahedrical M(2) sites in the mineral structure; no impurities of iron oxides were detected. The quite efficient deferration by HCl refluxing produced a substantial alteration of lamellar structure of montmorillonite, whilst dithionite/citrate treatment did not induce severe structural changes but had low iron removal efficiency.     

Ferroelectricity from iron valence ordering in rare earth ferrites?

The possibility of multiferroicity arising from charge ordering in LuFe₂O₄ and structurally related rare earth ferrites is reviewed. Recent experimental work on macroscopic indications of ferroelectricity and microscopic determination of coupled spin and charge order indicates that this scenario does not hold. Understanding the origin of the experimentally observed charge and spin order will require further theoretical work. Other aspects of recent research in these materials, such as geometrical frustration effects, possible electric‐field‐induced transitions, or orbital order are also briefly treated.

     

Mössbauer and magnetization studies of iron oxide nanocrystals

Monodisperse iron oxide nanocrystals have been produced following non-hydrolytic, thermal decomposition routes. Spherically shaped particles with diameter of 4 and 12 nm and cubic shaped particles with an edge length of 9 nm have been studied. The particles have been shown to consist of mainly maghemite. A reduction of the saturation magnetic hyperfine field is observed for the 4 nm particles as compared to the corresponding bulk value. The anisotropy energy determined from the temperature variation of the magnetic hyperfine field was strongly enhanced for the 4 nm particles.     

Chemical Synthesis of Highly Magnetic, Air-Stable Silica-Coated iron Particles

Highly magnetic and air-stable silica-coated Fe particles have been prepared by a rapid and simple method. The specific magnetization of the sample can be as high as 201 Am^2 /kg even including silica, which is a non-magnetic material. The iron particle coated with silica is passivated and protected from oxidation. The influences of H2 reduction temperature on structure and magnetic properties are also studied.     

A Mossbauer study of the magnetic coupling in iron phosphorous trisulfides

The polycrystalline sample of layered compound FePS_3 has been investigated by using M?ssbauer spectroscopy (12K to 300K), magnetic susceptibility measurements, x-ray diffraction and FTIR spectroscopy. The antiferromagnetic order exists below T_N=120.5±1K. The M?ssbauer spectra below T_N indicate that the magnetization axis is perpendicular to the layer of FePS_3, and the divalent iron cations are in their high spin configurations. By fitting the hyperfine field parameters near the Néel temperature, we obtain information on the nature of magnetic interactions in the material. The results show that the magnetic coupling can be treated by the two-dimensional Ising model, and it can be interpreted on the basis of a crystal-field effect.     

Mössbauer spectroscopy study of iron corrosion underneath painting system

The effect of pigments on the development of corrosion products between the painting system and metal surface when exposed to marine environments has been discussed. The pigments studied were; Red Mud Zinc chromate, Zinc chromate, Red oxide Zinc Phosphate, Manganese Phosphate Barium chromate and Basic Lead Silico Chromate. Mossbauer Spectroscopy revealed that the upper rust layer in all the cases consisted of-Fe203,-FeOOH and-FeOOH. The lower rust layer immediately in contact with the metal surface consisted of an asymmetrical doublet due to -FeOOH.     

Atomistic simulation of kink structure on edge dislocation in bcc iron

Based on the general theory of dislocation and kink, we have constructed the three kink models corresponding to the 1/2 （111）{011} and 1/2 （111）{112} edge dislocations （EDs） in bcc Fe using the molecular dynamics method. We found that the geometric structure of a kink depends on the type of ED and the structural energies of the atom sites in the dislocation core region, as well as the geometric symmetry of the dislocation core and the characteristic of the stacking sequence of atomic plane along the dislocation line. The formation energies and widths of the kinks on the 1/2 （111）{011} and 1/2 （111）{112} EDs are calculated, the formation energies are 0.05eV and 0.04eV, and widths are 6.02b and 6.51b, respectively （b is the magnitude of the Burgers vector）. The small formation energies indicate that the formation of kink in the edge dislocation is very easy in bcc Fe.