Bulk Iron Research Articles

Solvothermal preparation of iron nanosheets

Iron nanosheet has been prepared in the presence of N-Methylaniline by solvothermal method. The structural property of the sample has been studied by X-ray diffraction and transmission electron microscopy. The magnetic properties have been extensively investigated by hysteresis loops and temperature-dependent magnetization curves. XRD result exemplifies that the as-prepared product has been identified as iron with body centered cubic structure. TEM observation showed that the as-prepared product composed of sheet-like nanostructure with size was around 25 nm. FTIR result suggests that the N-Methylaniline molecules are on the surface of the Fe Nano sheet. Magnetic measurements showed that the prepared iron nanosheet was ferromagnetic behavior at 300 K. Compared with bulk iron, Fe nanosheet exhibits significant increase in coercive force due to the presence of shape anisotropy. Moreover, the temperature dependent magnetization curves show no blocking temperature up to 300 K, which indicates the prepared sheet, is ferromagnetic character at room temperature.

Interface atomic structures and magnetic anisotropy of Fe and Pd/Fe monatomic films on Pd(001)

The magnetic anisotropy of monatomic Fe films on Pd(001) with or without a Pd overlayer was investigated from the standpoint of interface atomic structures. Quantitative analysis included low-energy electron diffraction and x-ray magnetic circular dichroism (XMCD) experiments, and first-principles calculations were also performed on monatomic Fe and Pd/Fe systems. It was revealed that Fe atoms intermix with the Pd substrate at room temperature. A spin reorientation transition occurs at a critical Fe thickness of 1.2 monolayers (ML) in Fe/Pd(001), while in-plane magnetic anisotropy is persistent in Pd/Fe/Pd(001) throughout the entire sample. The Fe 3$d$ spin and orbital magnetic moments for both systems are strongly enhanced near 1 ML Fe thickness, as compared to those of the bulk iron crystal. In addition, an induced magnetic moment in interfacial Pd atoms was observed by XMCD at the Pd ${M}_{2,3}$ core absorption edges. It was concluded that the $L{1}_{0}$-like tetragonally distorted interface atomic structure in monatomic Fe/Pd(001) induces the perpendicular magnetic anisotropy.

Iron Solubility Related to Particle Sulfur Content in Source Emission and Ambient Fine Particles

The chemical factors influencing iron solubility (soluble iron/total iron) were investigated in source emission (e.g., biomass burning, coal fly ash, mineral dust, and mobile exhaust) and ambient (Atlanta, GA) fine particles (PM2.5). Chemical properties (speciation and mixing state) of iron-containing particles were characterized using X-ray absorption near edge structure (XANES) spectroscopy and micro-X-ray fluorescence measurements. Bulk iron solubility (soluble iron/total iron) of the samples was quantified by leaching experiments. Major differences were observed in iron solubility in source emission samples, ranging from low solubility (<1%, mineral dust and coal fly ash) up to 75% (mobile exhaust and biomass burning emissions). Differences in iron solubility did not correspond to silicon content or Fe(II) content. However, source emission and ambient samples with high iron solubility corresponded to the sulfur content observed in single particles. A similar correspondence between bulk iron solubility and bulk sulfate content in a series of Atlanta PM2.5 fine particle samples (N = 358) further supported this trend. In addition, results of linear combination fitting experiments show the presence of iron sulfates in several high iron solubility source emission and ambient PM2.5 samples. These results suggest that the sulfate content (related to the presence of iron sulfates and/or acid-processing mechanisms by H(2)SO(4)) of iron-containing particles is an important proxy for iron solubility.

Formation of nanoparticles during laser ablation of an iron target in a liquid

Formation of nanoparticles during laser ablation of a bulk iron target in water and isopropyl alcohol by pulsed near-IR laser radiation has been experimentally investigated. The experiments were performed using a 3-ns neodymium laser and a 100-ns ytterbium fibre laser. A size distribution function is obtained for the nanoparticles, which is peaking near 15 nm. The diffraction patterns of the nanoparticles exhibit pronounced peaks of metallic iron. An analysis of the nanoparticles by transmission electron microscopy shows that in some cases they have a core — shell structure. The nanoparticles formed by laser ablation have pronounced magnetic properties. The absorption spectra of colloids with iron nanoparticles contain peaks, which presumably correspond to the electron plasmon resonance in these particles.

Impact of phosphorus gettering parameters and initial iron level on silicon solar cell properties

ABSTRACTWe have studied experimentally the effect of different initial iron contamination levels on the electrical device properties of p‐type Czochralski‐silicon solar cells. By systematically varying phosphorus diffusion gettering (PDG) parameters, we demonstrate a strong correlation between the open‐circuit voltage (Voc) and the gettering efficiency. Similar correlation is also obtained for the short‐circuit current (Jsc), but phosphorus dependency somewhat complicates the interpretation: the higher the phosphorus content not only the better the gettering efficiency but also the stronger the emitter recombination. With initial bulk iron concentration as high as 2 × 1014 cm−3, conversion efficiencies comparable with non‐contaminated cells were obtained, which demonstrates the enormous potential of PDG. The results also clearly reveal the importance of well‐designed PDG: to achieve best results, the gettering parameters used for high purity silicon should be chosen differently as compared with for a material with high impurity content. Finally we discuss the possibility of achieving efficient gettering without deteriorating the emitter performance by combining a selective emitter with a PDG treatment. Copyright © 2012 John Wiley &amp; Sons, Ltd.

Theoretical Investigation of Hydrogen Adsorption and Dissociation on Iron and Iron Carbide Surfaces Using the ReaxFF Reactive Force Field Method

We have developed a ReaxFF reactive force field to describe hydrogen adsorption and dissociation on iron and iron carbide surfaces relevant for simulation of Fischer–Tropsch (FT) synthesis on iron catalysts. This force field enables large system (>>1000 atoms) simulations of hydrogen related reactions with iron. The ReaxFF force field parameters are trained against a substantial amount of structural and energetic data including the equations of state and heats of formation of iron and iron carbide related materials, as well as hydrogen interaction with iron surfaces and different phases of bulk iron. We have validated the accuracy and applicability of ReaxFF force field by carrying out molecular dynamics simulations of hydrogen adsorption, dissociation and recombination on iron and iron carbide surfaces. The barriers and reaction energies for molecular dissociation on these two types of surfaces have been compared and the effect of subsurface carbon on hydrogen interaction with iron surface is evaluated. We found that existence of carbon atoms at subsurface iron sites tends to increase the hydrogen dissociation energy barrier on the surface, and also makes the corresponding hydrogen dissociative state relatively more stable compared to that on bare iron. These properties of iron carbide will affect the dissociation rate of H2 and will retain more surface hydride species, thus influencing the dynamics of the FT synthesis process.

Synthesis and characterization of magnetic Fe/CNTs composites with controllable Fe nanoparticle concentration

Fe/CNTs composites, with different concentrations of Fe nanoparticles (NPs) on carbon nanotube (CNT) surfaces, were successfully fabricated via a facile solvothermal method. The lengths of CNTs are up to 10μm and the mean diameter of the Fe nanoparticles is about 25nm. The structures, composition and magnetic properties of the Fe/CNTs were characterized by XRD, FTIR, FE-SEM, TEM and PPMS. We found that the concentrations of Fe nanoparticles depositing on the CNTs could be controlled by adjusting the initial mass ratio of ferrocene to CNTs. The Fe/CNTs composites display good ferromagnetic properties at room temperature, with a saturation magnetization of 125emu/g-Fe and a coercivity of 276Oe. The Curie temperature of the sample is about 1038K, slightly lower than that (1043K) of the bulk iron.

Bacteriogenic Fe(III) (Oxyhydr)oxides Characterized by Synchrotron Microprobe Coupled with Spatially Resolved Phylogenetic Analysis

Ubiquitous presence of microbes in aquatic systems and their inherent ability of biomineralization make them extremely important agents in the geochemical cycling of inorganic elements. However, the detailed mechanisms of environmental biomineralization (e.g., the actual reaction rates, the temporal and spatial dynamics of these processes) are largely unknown, because there are few adequate analytical techniques to observe the biogenic oxidation/reduction reactions in situ. Here, we report a novel technical approach to characterize specific biominerals associated with a target microbe on high spatial resolution. The technique was developed by combining directly in situ phylogenetic analysis, fluorescence in situ hybridization (FISH), with a synchrotron microprobe method, micro X-ray absorption fine structure spectroscopy (μ-XAFS), and was applied to iron mineral deposition by iron(II)-oxidizing bacteria (IOB) in environmental samples. In situ visualization of microbes revealed that in natural iron mats, Betaproteobacteria dominated by IOB were dominantly localized within 10 μm of the surface. Furthermore, in situ chemical speciation by the synchrotron microprobe suggested that the Fe local structure at the IOB accumulating parts was dominantly composed of short-ordered Fe-O(6) linkage, which is not observed in bulk iron mat samples. The present study indicates that coupled XAFS-FISH could be a potential technique to provide direct information on specific biogenic reaction mediated by target microorganism.

Spin-polarized surface states on Fe-deposited Au(111) surface: A theoretical study

We have studied electronic structure of Fe-deposited Au(111) by performing ab initio density functional theory calculations. We find that the magnetic moment on the deposited Fe layer is enhanced as compared to that in bulk iron. We observe a large number of new states on the Fe-deposited surface — one of which is in the majority spin channel having similar dispersion to that on the clean surface, and others in the minority spin channel. The effective mass of electrons in surface states near the Fermi level increases on Fe deposition. The electronic properties are found to be insensitive to the stacking of near-surface layers. We need to use very thick slabs in our calculations to avoid splitting of surface states due to spurious interactions between the two surfaces of the slab. Using the local density of states profiles for different surface states, we conclude that in scanning tunneling microscope experiments one can detect two of the surface states — one in the majority channel below the Fermi level, and another in the minority channel appearing just above the Fermi energy. We compare our results to those from scanning tunneling spectroscopy experiments.

The cantilever beam magnetometer: A simple teaching tool for magnetic characterization

We have designed and fabricated an ex situ optical cantilever beam magnetometer to measure the magnetization and the magnetostriction of ferromagnetic materials. We discuss the working principle of a cantilever beam magnetometer and derive the theory of the cantilever bending due to magnetic torque acting on the sample attached to the cantilever substrate. We also present the results for bulk iron obtained using the cantilever beam magnetometer.

Electrical conductivity and dielectric relaxation of bulk iron (III) chloride tetraphenylporphyrin

The electrical conductivity and dielectric properties of bulk iron (III) chloride tetraphenylporphyrin, FeTPPCl, has been investigated in the frequency range from 40Hz to 5MHz and in the temperature range of 298–373K. The frequency dependence of σ(ω, T) follows the Jonscher's universal dynamic law. The temperature behaviour of the frequency exponents shows that the correlated barrier hopping (CBH) model is well adapted to FeTPPCl semiconductor material. The conductivity in the direct regime, σdc, is described by the variable range hopping (VRH). In spite of the absence of the dielectric loss peaks, application of the dielectric modulus formulism gives a simple method for evaluating the activation energy of the dielectric relaxation.

First-principles studies of the electronic properties of native and substitutional anionic defects in bulk iron pyrite

Systematic spin-polarized density functional theory calculations were performed to investigate the formation energies of native and substitutional anionic point defects in iron pyrite (FeS${}_{2}$) and their impact on bulk electronic structure. A detailed analysis indicates that neutral sulfur and iron vacancies do not act as efficient donors or acceptors. We find that substitutional oxygen does not induce gap states in pyrite and can actually passivate gap states created by sulfur vacancies. Most Group V and VII impurities create mid-gap states and produce spin polarization. In particular, Cl and Br are shallow donors that introduce delocalized spin-polarized electrons for potential use in photovoltaic and spintronics applications.

Thermal degradation pathways of nickel(II) bipyridine complexes to size-controlled nickel nanoparticles

Tris(bipyridine)nickel(II) chloride (1) and bis(bipyridine)nickel(II) chloride (2) pyrolize at heating rate of 50 °C/min to a maximum of 450 °C for 24 h under an inert atmosphere of flowing argon gas, to yield size-controlled nickel nanoparticles. Thermogravimetric studies of the complexes (1) and (2) and GC–MS analysis of the trapped volatile matter evolved during thermal degradation of the complexes indicate their clean decomposition pathway to zero-valent nickel. Both heating rate and argon gas flow rate affect purity, particle size, and shape of the particles. X-ray powder diffractometry and atomic force microscopy showed the formation of face-centered cubic (fcc) structured nickel particles having particle size in the range of 3.5–5.0 nm. Magnetic susceptibility measurements suggest nickel nanoparticles to be ferromagnetic in nature characterized by particle size–dependent Curie temperature and high coercivity that is comparable to the bulk iron.

High–Resolution Magnetic Field Measurement Using an STM–SQUID

Abstract We have developed an STM–SQUID microscope that combined a scanning tunneling microscope (STM) and a SQUID probe microscope for the purpose of high–resolution magnetic field measurement. We were able to obtain a spatial resolution of 1 μm or less by polishing the tip of the needle on the SQUID probe microscope to 100 nm or less, and by using a magnetic probe, which was the flux guide, as the STM probe. In this study, we took magnetic images of typical ferromagnetic materials, such as bulk iron and bulk nickel using the STM–SQUID microscope. We successfully observed the magnetic domain structures of these magnetic materials. However, topographic artifacts were also observed in the STM–SQUID images due to the background magnetic field from the sample. The future subject for resolution and quality improvement became clear.

Oxygen transport and isotopic exchange in iron oxide/YSZ thermochemically-active materials via splitting of C(18O)2 at high temperature studied by thermogravimetric analysis and secondary ion mass spectrometry

Ferrites are promising materials for enabling solar-thermochemical cycles for the production of synthetic fuels. Such cycles utilize solar-thermal energy for the production of hydrogen from water, or carbon monoxide from carbon dioxide. Recent work studying the thermochemical behaviour of iron oxides co-sintered with yttria-stabilised zirconia (YSZ) using thermogravimetric analysis revealed a striking difference in behaviour of iron that is in solid solution with the YSZ and that which exists as a second iron oxide phase. Materials in which the majority of iron was dissolved in the YSZ exhibited enhanced utilization of iron over those which possessed larger fractions of un-dissolved, bulk iron oxides. To illuminate this phenomena further, several samples of thermally-reduced iron oxide/8YSZ were re-oxidised using isotopically labelled C(18O)2. Post mortem characterization by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), with the application of multivariate analysis tools, enables the differentiation between 18O and 16O signals emanating from iron oxide particles. The distribution of 18O is uniform throughout the iron-doped 8YSZ, but concentrated at the surface of iron oxide particles embedded in this matrix. After identical thermal reduction and re-oxidation treatments, the gradient of 18O/16O across the iron oxide particles is found to depend on the size of the iron oxide particles, as well as the method of synthesis of the iron oxide/YSZ material. Comparative thermogravimetric analyses of the 18O-labelled materials and analogous un-labelled materials revealed that exposure to CO2 at 1100 °C results in rapid oxygen isotopic exchange.

Iron isotope composition of some Archean and Proterozoic iron formations

Fe isotopes can provide new insight into redox-dependent biogeochemical processes. Precambrian iron formations (IF) are deserving targets for Fe isotope studies because they are composed predominantly of authigenic Fe phases and record a period of unprecedented iron deposition in Earth’s history. We present Fe isotope data for bulk samples from 24 Archean and Proterozoic IF and eight Phanerozoic Fe oxide-rich deposits. These data reveal that many Archean and early Paleoproterozoic iron formations were a sink for isotopically heavy Fe, in contrast to later Proterozoic and Phanerozoic Fe oxide-rich rocks. The positive δ56Fe values in IF are best explained by delivery of particulate ferric oxides formed in the water column to the sediment–water interface. Because IF are a net sink for isotopically heavy Fe, there must be a corresponding pool of isotopically light Fe in the sedimentary record. Earlier work suggested that Archean pyritic black shales were an important part of this light sink before 2.35 billionyears ago (Ga). It is therefore likely that the persistently and anomalously low δ56Fe values in shales are linked with the deposition of isotopically heavy Fe in IF in the deeper parts of basins. IF deposition produced a residual isotopically light dissolved Fe pool that was captured by pyritic Fe in shales. Local dissimilatory Fe reduction in porewater and associated diagenetic reactions resulting in pyrite and carbonate precipitation may have further enhanced Fe isotope heterogeneity in marine sediments, and an ‘iron shuttle’ may have transported isotopically light Fe from shelf sediments to the basin. Nevertheless, water-column processing of hydrothermally delivered Fe likely had the strongest influence on the bulk iron isotope composition of Archean and Paleoproterozoic iron formations and other marine sediments.

Fast microbial reduction of ferrihydrite colloids from a soil effluent

Recent studies on the microbial reduction of synthetic iron oxide colloids showed their superior electron accepting property in comparison to bulk iron oxides. However, natural colloidal iron oxides differ in composition from their synthetic counterparts. Besides a potential effect of colloid size, microbial iron reduction may be accelerated by electron-shuttling dissolved organic matter (DOM) as well as slowed down by inhibitors such as arsenic. We examined the microbial reduction of OM- and arsenic-containing ferrihydrite colloids. Four effluent fractions were collected from a soil column experiment run under water-saturated conditions. Ferrihydrite colloids precipitated from the soil effluent and exhibited stable hydrodynamic diameters ranging from 281 (±146)nm in the effluent fraction that was collected first and 100 (±43)nm in a subsequently obtained effluent fraction. Aliquots of these oxic effluent fractions were added to anoxic low salt medium containing diluted suspensions of Geobacter sulfurreducens. Independent of the initial colloid size, the soil effluent ferrihydrite colloids were quickly and completely reduced. The rates of Fe2+ formation ranged between 1.9 and 3.3fmolh−1cell−1, and are in the range of or slightly exceeding previously reported rates of synthetic ferrihydrite colloids (1.3fmolh−1cell−1), but greatly exceeding previously known rates of macroaggregate-ferrihydrite reduction (0.07fmolh−1cell−1). The inhibition of microbial Fe(III) reduction by arsenic is unlikely or overridden by the concurrent enhancement induced by soil effluent DOM. These organic species may have increased the already high intrinsic reducibility of colloidal ferrihydrite owing to quinone-mediated electron shuttling. Additionally, OM, which is structurally associated with the soil effluent ferrihydrite colloids, may also contribute to the higher reactivity due to increasing solubility and specific surface area of ferrihydrite. In conclusion, ferrihydrite colloids from soil effluents can be considered as highly reactive electron acceptors in anoxic environments.

Synthesis of alcohols from CO and H2 on iron catalysts containing carbon fiber

It was found that alcohols can be synthesized from CO and H2 at 3 MPa and 280–300°C in the presence of Fe catalysts containing an activated fibrous carbon material (AFCM) as a support. It was established that 20% Fe/AFCM catalysts possess an extremely high specific activity in the conversion of carbon monoxide (∼1 × 10−4 mol CO (mol Fe)−1 s−1), which is higher than the activity of traditional bulk iron catalysts by almost an order of magnitude. The values of CO conversion and selectivity for alcohols obtained for these catalysts are close to the parameters of industrial processes (Synol process, Oxyl process, and synthesis according to Bashkirov); however, they are obtained under milder conditions in a single run rather than with the use of a recycle. The Fe/AFCM catalysts make it possible to obtain monohydric alcohols in yields to ∼50 g/m3 (to a 50% concentration in synthesis water) upon the almost complete conversion of CO. In this case, the fraction of C2-C4 alcohols was as high as 55–60%.

표면 자기광 커 효과의 이해

지난 20여년간 표면자성 현상의 연구에 가장 도움이 많이 되었던 실험방법중 하나인 표면 자기광 커효과(Surface magneto-optic Kerr effect, SMOKE) 실험 방법을 소개하고자 한다. 예를 들어 단일층의 철막이 강자성이 되는지, 또 큐리(Curie)온도는 bulk와 비교하여 얼마나 떨어져 있는지, 자화 용이축(easy-axis)은 어느 방향인지 등 매우 기본적인 자성박막의 특성은 스핀트로닉스(spintronics) 분야의 연구에 가장 기본적인 정보이다. 표면 자기광 커 효과(SMOKE)는 이러한 물음에 대한 답을 줄 수 있는 매우 효율적인 방법이다. We will introduce the surface magneto-optic Kerr effect (SMOKE), which is one of the most helpful experimental methods in the area of surface magnetism for the last two decades. The basic magnetic characteristics of magnetic thin film is the most essential part for the further understanding and application. For example, the possibility of the realization of ferromagnetism for a single layer of iron, its Curie temperature far below that of bulk iron, and the direction of easy axis are the fundamental questions for the spintronic application. SMOKE is an efficient method to answer for the questions above.

Confirmation of mass-independent Ni isotopic variability in iron meteorites

We report high-precision analyses of internally-normalised Ni isotope ratios in 12 bulk iron meteorites. Our measurements of 60Ni/ 61Ni, 62Ni/ 61Ni and 64Ni/ 61Ni normalised to 58Ni/ 61Ni and expressed in parts per ten thousand (‱) relative to NIST SRM 986 as ε 60 Ni 58 61 , ε 62 Ni 58 61 and ε 64 Ni 58 61 , vary by 0.146, 0.228 and 0.687, respectively. The precision on a typical analysis is 0.03‱, 0.05‱ and 0.08‱ for ε 60 Ni 58 61 , ε 62 Ni 58 61 and ε 64 Ni 58 61 , respectively, which is comparable to our sample reproducibility. We show that this ‘mass-independent’ Ni isotope variability cannot be ascribed to interferences, inaccurate correction of instrumental or natural mass-dependent fractionation, fractionation controlled by nuclear field shift effects, nor the influence of cosmic ray spallation. These results thus document the presence of mass-independent Ni isotopic heterogeneity in bulk meteoritic samples, as previously proposed by Regelous et al. (2008) (EPSL 272, 330–338), but our new analyses are more precise and include determination of 64Ni. Intriguingly, we find that terrestrial materials do not yield homogenous internally-normalised Ni isotope compositions, which, as pointed out by Young et al. (2002) (GCA 66, 1095–1104), may be the expected result of using the exponential (kinetic) law and atomic masses to normalise all fractionation processes. The certified Ni isotope reference material NIST SRM 986 defines zero in this study, while appropriate ratios for the bulk silicate Earth are given by the peridotites JP-1 and DTS-2 and, relative to NIST SRM 986, yield deviations in ε 60 Ni 58 61 , ε 62 Ni 58 61 and ε 64 Ni 58 61 of −0.006‱, 0.036‱ and 0.119‱, respectively. There is a strong positive correlation between ε 64 Ni 58 61 and ε 62 Ni 58 61 in iron meteorites analyses, with a slope of 3.03 ± 0.71. The variations of Ni isotope anomalies in iron meteorites are consistent with heterogeneous distribution of a nucleosynthetic component from a type Ia supernova into the proto-solar nebula.