Nanocrystalline Iron Research Articles

Studies on decontamination of cadmium rich water by a novel nano Iron oxide adsorbent

Synthesizing non-toxic adsorbent for abatement of hazardous pollutants from water is important to develop safe environment. In this study, nanocrystalline iron oxide particles were synthesized and utilized as effective nanoadsorbent for removing cadmium through adsorption. The as-prepared nanoadsorbent was characterized using sophisticated techniques. The objective of this study was to improve cadmium adsorption from aqueous solutions under a variety of conditions. With the help of Box-Behnken design, adsorption parameter settings were improved. Response Surface Methodology analysis was conducted to optimize the adsorption conditions, including pH, initial concentration of metal ions, and adsorbent dose. Comparisons were made between the optimal equations for linear and non-linear kinetics, along with isotherm models. Origin's curve fitting tool and the Solver add-in of Microsoft Excel are two non-linear analytical tools. The obtained results showed that the Origin curve fitting tool is superior to solver add in's error analysis method for determining isotherm parameters. The equilibrium data for cadmium removal using nano iron oxide/hydroxide adsorbent was best fitted to Langmuir isotherm model. The adsorption of cadmium was well described by the pseudo-second-order model. The study shows that the system appears to be spontaneous according to the Langmuir constant method and thermodynamic parameter via partition.

Insight into the effect of vibration parameters on deformation mechanism during scratching of nanograin iron alloy by molecular dynamics

Molecular dynamics simulations were employed to study the deformation behavior and microstructure evolution of nanocrystalline iron alloy during vibration-assisted scratching. The mechanical properties of the plastic deformation layer after scratching were tested by uniaxial tension. The results show that dislocation multiplication and twinning occur sequentially during loading, while dislocation rebound and detwinning occur during unloading. High stress induces dislocation multiplication. High strain rate facilitates the formation of deformation twins. Under the inhibitory effect of deformation twins on dislocation activity and the elastic recovery of the surface, dislocation density decreases with increasing frequency but initially increases and decreases with increasing amplitude. The plastic deformation layer at 10 GHz frequency and 1 nm amplitude exhibits optimal yield strength due to dislocation and nanotwin strengthening.

Enhanced Thermal Stability of Carbonyl Iron Nanocrystalline Microwave Absorbents by Pinning Grain Boundaries with SiBaFe Alloy Nanoparticles

Nanocrystalline carbonyl iron (CI) particles are promising microwave absorbents at elevated temperature, whereas their excessive grain boundary energy leads to the growth of nanograins and a deterioration in permeability. In this work, we report a strategy to enhance the thermal stability of the grains and microwave absorption of CI particles by doping a SiBaFe alloy. Grain growth was effectively inhibited by the pinning effect of SiBaFe alloy nanoparticles at the grain boundaries. After heat treatment at 600 °C, the grain size of CI particles increased from ~10 nm to 85.1 nm, while that of CI/SiBaFe particles was only 32.0 nm; with the temperature rising to 700 °C, the grain size of CI particles sharply increased to 158.1 nm, while that of CI/SiBaFe particles was only 40.8 nm. Excellent stability in saturation magnetization and microwave absorption was also achieved in CI/SiBaFe particles. After heat treatment at 600 °C, the flaky CI/SiBaFe particles exhibited reflection loss below −10 dB over 7.01~10.11 GHz and a minimum of −14.92 dB when the thickness of their paraffin-based composite was 1.5 mm. We provided a low-cost and efficient kinetic strategy to stabilize the grain size in nanoscale and microwave absorption for nanocrystalline magnetic absorbents working at elevated temperature.

Nanocrystalline Iron Oxides with Various Average Crystallite Size Investigated Using Magnetic Resonance Method

A series of nanocrystalline iron oxide samples (M1–M5) which differ from each other in average crystallite size (from 26 to 37 nm) was studied. The raw material was nanocrystalline iron with an average crystallite size equal to 21 nm promoted with hardly reducible oxides: Al2O3, CaO, K2O (in total, max. 10 wt%). Nanocrystalline iron was subjected to oxidation with water vapor to achieve different oxidation degrees (α = 0.16–1.00). Metallic iron remaining in the samples after the oxidizing step was removed by etching. Magnetic resonance spectra of all samples were obtained at room temperature. All resonance lines were asymmetric and intense. These spectra were fitted by Lorentzian and Gaussian functions. All spectral parameters depend on the preparation method of the nanoparticles. We suppose that the Lorentz fit gives us a spectrum from larger agglomerated sizes whereas the Gaussian fit comes from much smaller magnetic centers. For the nanocrystalline samples with the largest size of iron oxide nanocrystallites, the highest value of total integrated intensity was obtained, indicating that at smaller sizes, they are more mobile in reorientation processes resulting in more settings of anti-parallel magnetic moments. The magnetic anisotropy should also increase with the increase in size of nanocrystallites.

Hydrolysis Products of Fe(III)‐Si Systems With Different Si/(Si + Fe) Molar Ratios: Implications to Detection of Ferrihydrite on Mars

AbstractFerrihydrite, a nanocrystalline iron (oxyhydr)oxide mineral, is widely distributed in soils and sediments on Earth and is probably an important component and/or precursor of widespread nanophase iron minerals on Mars. Terrestrial ferrihydrite often co‐occurs with amorphous silica and/or contains a certain amount of Si in its structure. However, it remains ambiguous how environmental Si concentration affects the formation‐evolution and structure‐spectral features of ferrihydrite in the Fe(III)‐Si systems. To this end, hydrolysis experiments were carried out for Fe‐Si systems at an unprecedentedly wide range of initial Si/(Fe + Si) molar ratios (0–0.80), followed by characterizing the products detailly. X‐ray diffraction, Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, Mössbauer spectroscopy, and transmission electron microscopy results showed that at Si/(Fe + Si) molar ratios ≤0.30, the main phase of the products was ferrihydrite, of which the unit cells enlarged, the crystallinity decreased, and the existing state of Fe changed with increased Si contents; at Si/(Fe + Si) molar ratios ≥0.40, ferrihydrite was no longer formed and a novel amorphous Fe‐O‐Si phase was instead obtained, with the excess Si forming amorphous silica. The visible and near‐infrared spectroscopy, the most powerful tool to detect hydrous minerals on the surface of Mars at global or regional scales, showed weakness in identifying ferrihydrite‐like materials obtained in the Fe‐Si systems. Raman spectroscopy can identify ferrihydrite and Si‐containing ferrihydrite but cannot differentiate between them. Mössbauer spectroscopy showed great potential in both identifying and differentiating between ferrihydrite and Si‐containing ferrihydrite, and thus can be used to characterize the poorly ordered iron (oxyhydr)oxides on Mars.

Nanocrystalline FeMnO3 Powder as Catalyst for Combustion of Volatile Organic Compounds.

The paper shows the obtaining of nanocrystalline iron manganite (FeMnO3) powders and their investigation in terms of catalytic properties for a series of volatile organic compounds. The catalyst properties were tested in the catalytic combustion of air-diluted vapors of ethanol, methanol, toluene and xylene at moderate temperatures (50-550 °C). Catalytic combustion of the alcohols starts at temperatures between 180 °C and 230 °C. In the case of ethanol vapors, the conversion starts at 230 °C and increases rapidly reaching a value of around 97% at 300 °C. For temperatures higher than 300 °C, the degree of conversion is kept at the same value. In the case of methanol vapors, the conversion starts at a slightly lower temperature (180 °C), and the degree of conversion reaches the value of 97% at a higher temperature (440 °C) than in the case of ethanol, and it also remains constant as the temperature increases. Catalytic combustion of the hydrocarbons starts at lower temperatures (around 50 °C), the degree of conversion is generally lower, and it increases proportionally with the temperature, with the exception of toluene, which shows an intermediate behavior, reaching values of over 97% at 430 °C. The studied iron manganite can be recommended to achieve catalysts that operate at moderate temperatures for the combustion of some alcohols and, especially, ethanol. The performance of this catalyst with regard to ethanol is close to that of a catalyst that uses noble metals in its composition.

The Effect of Impact Load on the Atomistic Scale Fracture Behavior of Nanocrystalline bcc Iron.

Nanocrystalline metals have many applications in nanodevices, especially nanoscale electronics in aerospace. Their ability to resist fracture under impact produced by environmental stress is the main concern of nanodevice design. By carrying out molecular dynamics simulations under different fast loading rates, this work examines the effect of impact load on the fracture behavior of nanocrystalline bcc iron at an atomistic scale. The results show that a crack propagates with intergranular decohesion in nanocrystalline iron. With the increase in impact load, intergranular decohesion weakens, and plastic behaviors are generated by grain boundary activities. Also, the mechanism dominating plastic deformation changes from the atomic slip at the crack tip to obvious grain boundary activities. The grain boundary activities produced by the increase in impact load lead to an increase in the threshold energy for crack cleavage and enhance nanocrystalline bcc iron resistance to fracture. Nanocrystalline bcc iron can keep a high fracture ductility under a large impact load.

Thermodynamics of Iron Ammonia Synthesis Catalyst Sintering

The sintering of iron ammonia synthesis catalysts (nanocrystalline iron promoted with: Al2O3, CaO and K2O) was studied under a hydrogen atmosphere, in a temperature range of 773 to 973 K to obtain stationary states. The catalysts were characterized by measuring the nitriding reaction rate under an ammonia atmosphere at 748 K to obtain steady states and the measurement of specific surface area. Chemical processes were conducted in a tubular differential reactor enabling thermogravimetric measurements and the chemical composition analysis of a gas phase under conditions allowing experiments to be carried out in the kinetic region of chemical reactions. An extended model of the active surface of the iron ammonia synthesis catalyst was presented, taking into account the influence of the gas phase composition and process temperature. The surface of iron nanocrystallites was wetted using promoters in an exothermic process associated with the formation of the surface Fes-O- bond and the change in the surface energy of iron nanocrystallites. Promoters formed on the surface of iron nanocrystallites with different structures of chemisorbed dipoles, depending on the composition of the gas phase. The occupied sites stabilized the structure, and the free sites were active sites in the process of adsorption of chemical reagents and in sintering. Based on the bonding energy of the promoter oxides and the difference in surface energy between the covered and uncovered surfaces, the wetting abilities of promoters, which can be arranged according to the order K2O > Fe3O4 > Al2O3 > CaO, were estimated. By increasing the temperature in the endothermic sintering process, the degree of surface coverage with dipoles of promoters decreased, and thus the catalyst underwent sintering. The size distribution of nanocrystallites did not change with decreasing temperature. Only the equilibrium between the glass phase and the surface of iron nanocrystallites was then established.

Temperature-dependent void nucleation and growth in single-crystal and nanocrystalline iron at extreme strain rates: atomistic insights

In this paper, we use molecular dynamics simulation with the embedded atomic method to perform triaxial deformation experiments on single-crystal and nanocrystalline iron at a strain rate of 5×10−9 s−1 and investigate the temperature effect on the void nucleation and growth process. We also evaluate the applicability of the Nucleation And Growth (NAG) model for single-crystal iron. The results indicate that the maximum tensile stress of both single-crystal and nanocrystalline iron decreases as temperature increases, with a reduction of 35.9% for single-crystal iron and 36.2% for nanocrystalline iron from 100 K to 1100 K. It is demonstrated that void nucleation and growth is more favored at high temperature. The void nucleation and growth process in single-crystal iron under high strain rate follows the NAG model. We analyze the sensitivity of the NAG parameters at different temperatures and find that the void nucleation and growth threshold of single-crystal iron is much higher than that of low carbon steel. The results can provide insights for developing fracture models of iron at extremely high strain rate and describing the dynamic damage at continuum length scales.

Nanoscale Kirkendall shift in thin films studied using x-ray waveguide structures

Kirkendall effect has played an important role in developing the understanding of atomic diffusion and mass transport in solids. In thin films and multilayers, in which the microstructure may be far from thermal equilibrium, behavior of a system can be very different from that of the bulk. Therefore, there is a great need to understand the peculiarities of Kirkendall shift occurring at nanometer or sub-nanometer length scale in such systems. In the present work, Kirkendall shift in thin films has been measured with sub-nanometer accuracy, by making use of x-ray planar waveguide structures. Using this technique, we report an apparently counterintuitive result of Kirkendall shift associated with self-diffusion in nanocrystalline iron. The cavity of the waveguide consists of two layers of iron having different microstructures, separated by a thin marker layer of Ag. Thermal annealing results in shift of the Ag marker towards the Fe layer having a coarser grain structure. The effect is established unambiguously by studying two samples with the order of the two Fe layers reversed, and a third sample with the two Fe layers having the same microstructure. The result can be understood in terms of the difference in the microstructure of the two Fe layers; difference in the grain size and hence different concentration of the grain boundaries in the two layers results in a net mass transfer from one region to the other.

Nanocrystalline iron hydroxide lignocellulose filters for arsenate remediation.

Harmful levels of environmental contaminants, such as arsenic (As), persist readily in the environment, threatening safe drinking water supplies in many parts of the world. In this paper, we present a straightforward and cost-effective filtration technology for the removal of arsenate from potable water. Biocomposite filters comprised of nanocrystalline iron oxides or oxyhydroxides mineralized within lignocellulose scaffolds constitute a promising low cost, low-tech avenue for the removal of these contaminants. Two types of iron oxide mineral phases, 2-line ferrihydrite (Fh) and magnetite (Mt), were synthesized within highly porous balsa wood using an environmentally benign modification process and studied in view of their effective removal of As from contaminated water. The mineral deposition pattern, minerology, as well as crystallinity, were assessed using scanning electron microscopy, transmission electron microscopy, micro-computed X-ray tomography, confocal Raman microscopy, infrared spectroscopy, and X-ray powder diffraction. Our results indicate a preferential distribution of the Fh mineral phase within the micro-porous cell wall and radial parenchyma cells of rays, while Mt is formed primarily at the cell wall/lumen interface of vessels and fibers. Water samples of known As concentrations were subjected to composite filters in batch incubation and gravity-driven flow-through adsorption tests. Eluents were analyzed using microwave plasma optical emission spectroscopy (MP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). By subjecting the filters to a flow of contaminated water, the time for As uptake was reduced to minutes rather than hours, while immobilizing the same amount of As. The retention of As within the composite filter was further confirmed through energy-dispersive X-ray mappings. Apart from addressing dangerously high levels of arsenate in potable water, these versatile iron oxide lignocellulosic filters harbor tremendous potential for addressing current and emerging environmental contaminants that are known to adsorb on iron oxide mineral phases, such as phosphate, polycyclic aromatic hydrocarbons or heavy metals.

Structural, magnetic, antimicrobial and hemolysis properties of sol–gel derived iron manganese tri oxide (FeMnO3) nanostructures

Nanocrystalline Iron Manganese Tri Oxide (FeMnO3, abbreviation name IMTO) material was attempted via colloidal solution followed by gel formation and subsequent processing at a calcined temperature of 480 °C. The above-mentioned compound was investigated for its structural characteristics, magnetic behavior, antibacterial response, and hemolysis experiment for spintronics and biomedical applications. The cubic crystal structure and weak ferromagnetic behaviour were noticed for the synthesized material from the powder X-ray diffraction (XRD) pattern and Vibrating Sample Magnetometer (VSM) studies. The surface structure of the title compound is noticed in aggregated spherical particles using Scanning Electron Microscopy (SEM) analysis. The antimicrobial activity of IMTO samples against gram-positive strains such as Streptococcus mutans (S. mutans) and Staphylococcus aureus (S. aureus) and gram-negative strains like Escherichia coli (E. coli) and Pseudomonas aeruginosa (P. aeruginosa) has been performed, followed by measurements of the zone of inhibition and their values are elucidated in detail. The hemolysis assay was carried out by taking human blood with the synthesized compound at various concentrations (5, 10, and 15 mg/mL), and the results showed its biocompatible nature.

Chemical vapor synthesis of nanocrystalline iron oxides

Chemical vapor synthesis (CVS) is a gas phase process to generate nanoparticles via a chemical reaction. In this contribution a review of recent methodological advances is provided using nanocrystalline iron oxides as model system. Novel methods are described to control precursor flow of sublimating metalorganic solids, characterization of electronic and molecular structure of vapors using X-ray absorption spectroscopy (XAS), in situ determination of oxygen partial pressure, variation of the time-temperature profile, in situ characterization of electronic, local, crystal and micro-structure using XAS, wide and small angle scattering (WAXS and SAXS) and finally methods to design the CVS process and materials development.

Nanocrystalline Iron Pyrophosphate-Regulated Amorphous Phosphate Overlayer for Enhancing Solar Water Oxidation

HighlightsInducing a localized crystalline iron pyrophosphate in amorphous iron phosphate overlayer.Enhanced photoelectrochemical water oxidation activity with long-term durability.The heterogeneous hybrid structure overcoming the energy barrier in water oxidation.

Differentiation of fine-textured podzolic soils controlled by climate and landscape in Taiwan

Podzolization is considered to be facilitated by factors such as cool and humid climate, sufficient supply of certain types of organic acids, and coarse-textured parent materials. However, podzolic soils in subalpine areas in Taiwan are characterized by clay content higher than 30%, which differed from that in typical podzolic soils in temperate and boreal regions. This study examined the importance of factors controlling the differentiation of fine-textured podzolic soils in Taiwan. Samples from 31 pedons were examined in this study, and the pedons were grouped into four types, namely Spodosols, Ultisols, Inceptisols, and Inceptisols with placic horizons. Soil colors with 7.5YR 5/6 (the accumulation of spodic materials) and micromorphological observation of oriented clay coatings in the Spodosols confirmed the occurrence of podzolization and clay illuviation, and the selective extraction of Fe and Al confirmed that the Spodosols (Type I) had a higher accumulation of organometallic complexes than the other podzolic soils. A two-step mechanism, namely (1) clay illuviation at an early stage of pedogenesis and (2) podzolization after the canopy vegetation formed, was proposed for the formation of fine-textured Spodosols. Photomicrographs of the Ultisols (Type II) displayed clay hypocoatings masked by spodic materials, and argillic horizons were characterized by a high amount of nanocrystalline iron and high optical density of the oxalate extract. However, the accumulated nanocrystalline iron oxides in the Ultisols were due to the degradation of organic matter under high summer temperatures. Moreover, the leaching of iron in the albic horizons of the Ultisols was attributed to episaturation caused by high clay contents. The Inceptisols (Type III) were transitional soils before forming the Spodosols or the Ultisols, and high clay contents further induced episaturation and formed placic horizons in the Inceptisols (Type IV). Principal component analysis revealed that soil texture and precipitation were the main factors controlling the differentiation of podzolic soils in Taiwan. These factors determined the penetrability and leaching potential of soils, and only the coarse-textured soils with higher leaching potential had the chance of developing Spodosols. However, the developments of Ultisols and Inceptisols with placic horizons were controlled by air temperature and landscape, namely elevation and slope. The bleached E horizons in podzolic Ultisols were attributed to their flat landscape, which favored episaturation and caused the reduction of iron. Low elevation and high temperature in these regions also facilitated the degradation of organic matter and the accumulation of nanominerals.

Formation of polymorphs and pores in small nanocrystalline iron oxide particles

A novel chemical vapor synthesis reactor design is used to control the pore-particle mesostructure and investigate the pore formation mechanism through the variation of residence time in oxygen. This enables the exploitation of the Kirkendall effect at the nanoscale to generate ultrasmall pores in small nanocrystalline iron oxide particles. Detailed structural characterization and quantitative data analysis of complementary high resolution transmission electron microscopy images, X-ray diffractograms, nitrogen sorption isotherms and X-ray absorption spectra provide a consistent comprehensive picture of the hollow nanoparticles from the local to the microstructure. The pore formation mechanism seems to play a key role for β-Fe2O3 polymorph formation.

Influence of the size of iron nanoclusters on their magnetization

The size of iron nanocrystals significantly affects the value of their magnetization. However, an adequate model of the structure of nanocrystalline formations comprising different numbers of iron atoms still does not exist. In this work, spatial models of nanocrystalline iron clusters differing in configuration and the number of their constituent atoms are constructed. Tetrahedrally close-packed cluster assemblies of iron atoms are taken as the basis for the proposed structures of nanocrystals. The spectra of the density of electronic states for the proposed clusters are constructed using the theory of the electron density functional. The calculation was carried out by the method of scattered waves in accordance with the band theory of crystals. The appearance of magnetization in tetrahedral close-packed cluster formations is associated with excited electronic states of atoms located on the surface of the nanocluster. Excited atoms have an increased electron density, that is, electrons are able to transition to states with higher energy, approaching the Fermi energy. In this case, the Stoner criterion necessary for the occurrence of magnetization is fulfilled. The configurations of electrons with spin up and down differ, which is why uncompensated magnetic moments appear. It is shown that the proposed models of iron nanoclusters are in satisfactory agreement with the known experimental data.

Eddy current and magnetic evaluation of nanostructured iron–cobalt produced by ball-milling

The nanocrystalline iron (Fe)–cobalt (Co) alloy exhibits significant properties compared with a conventional material of the same concentration due to the impact of the crystal size. Nanocrystalline FeCo was synthesized from elementary iron and cobalt powdered materials using a planetary ball mill. The complete formation of the iron–cobalt solid solution was observed after 10 h of grinding, and the crystal size reached 15 nm with a grinding time of 40 h. This research aims to investigate the electromagnetic properties of the iron–cobalt nanocrystalline system. Structural and morphological evaluations were carried out using X-ray diffraction and scanning electron microscopy, respectively. The change in electromagnetic behavior was analyzed by using the eddy current technique, which confirms that the nanostructural state can be verified by using the impedance spectrum. The magnetic results found by the vibrating-sample magnetometry measurements confirm those found by the eddy current tests.

Insight into defect cluster annihilation at grain boundaries in an irradiated nanocrystalline iron

The design of radiation-tolerant polycrystalline materials has been mainly based on the control and manipulation of grain boundaries (GBs) that leads to annihilation of point defects at grain-boundary neighborhoods thus resulting in the formation of defect denuded zones. Nanocrystalline materials are potential candidates providing large density defect sinks for individual point defects and small highly mobile defect clusters (DCs). Using the in-situ irradiation transmission electron microscopy (TEM) technique, this study not only experimentally revealed the coalescence of small glissile DCs at/near GB and their subsequent annihilation at grain-boundary, but also provide insight into defect cluster dynamics. The small DCs were found to be transported to grain-boundary neighborhoods where they can annihilate by the one-dimensional loop hop or Burgers-vector rotation mechanism to GBs, considered as the main contribution to the long-range flux of interstitials to GB sinks. This process had marked effects on the morphology of the irradiated microstructure in nanocrystalline iron, limiting the length of DC strings and reducing the coalescence of DCs into large clusters (dislocation loops).

Examination of critical grain size of isotropic nanocrystalline iron through molecular dynamics analysis

ABSTRACT The critical grain size for isotropic nanocrystalline pure iron was investigated utilizing Molecular Dynamics (MD). First, number of grains required for isotropic behaviour was determined utilizing statistically significant grain counts – alleviating challenges faced in simulation of nanocrystalline materials. The current investigation provides a thorough guideline for simulating isotropic nanocrystalline materials. Second, an investigation into the effect of strain rate was performed to demonstrate its effect on mechanical properties of pure, isotropic nanocrystalline iron. Next, the critical grain size of pure nanocrystalline iron was investigated, indicating the change from Hall-Petch to inverse Hall-Petch. It was shown that MD of an isotropic pure nanocrystalline iron structure possessed a clearly defined critical grain size through examination of flow stress and maximum stress. It was shown that neither elastic modulus nor Poisson’s ratio were viable indicators for a critical grain size, instead, both tended towards their macroscale equivalent. Alternatively, yield stress may be viable, but was not recommended due to varying definitions for what exactly constitutes the yield point. Lastly, an investigation into the microstructure was performed near the critical grain size and at the extremes of grain sizes investigated. This highlighted the microstructural behaviour within both Hall-Petch and inverse Hall-Petch regimes throughout straining.