A study of Fe--N alloy systems

Magnetic properties of Fe nitrides have been reexamined by ⁵⁷Fe Mössbauer spectroscopy. Hyperfine magnetic fields for α″-Fe₁₆N₂, γ′-Fe₄N, ε-Fe₃N, ζ-Fe₂N, NaCl-type FeN and ZnS-type FeN have been determined at various temperatures. Although α′-, γ″-, and ε-nitride are all ferromagnets, ζ-Fe₂N is found to be an antiferromagnet below 9 K and ZnS-type FeN is non-magnetic at 4.2 K. Contrary to the ZnS-type FeN, the NaCl-type FeN is an antiferromagnet and shows a component with a surprisingly large hyperfine magnetic field of 49 T.     

Mixing characterization of mechanically milled Fe75Si15M10 powders using Mössbauer spectroscopy

Iron nitrides are attractive as they show excellent magnetic properties which can be utilized as recording and permanent magnetic materials for potential applications. Due to the high saturation magnetization and chemical stability, γ ^′-Fe₄N compound is widely investigated as a promising high density magnetic recording material. γ ^′-Fe₄N particles were synthesized by conventional gaseous nitriding in a heated atmosphere containing ammonia as a source of nitrogen. X-ray diffraction, ⁵⁷Fe Mössbauer spectroscopy, vibrating sample magnetometer, scanning electron microscopy and transmission electron microscopy are used for the characterization of the as prepared sample.     

Exchange bias behavior of monodisperse Fe3O4/γ-Fe2O3 core/shell nanoparticles

We have carried out systematic studies on well-characterized monodisperse Fe₃O₄/γ-Fe₂O₃ core/shell nanoparticles of 2-30 nm having a very narrow size distribution and possessing a uniquely mono-layer of surface γ-Fe₂O₃. This unique core-shell structure, probably having a disordered magnetic surface state, leads us to three key observations of unusual magnetic properties: i) a very large magnetic exchange anisotropy reaching over 7 × 10⁶ erg/cm³ for the smaller particles, ii) exchange bias behavior in the magnetization data of the core/shell Fe₃O₄/γ-Fe₂O₃ nanoparticles, and iii) the temperature dependence of the coercive field following an unusual exponential behavior.     

Mössbauer investigations of Fe and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles for hyperthermia applications

Magnetic nanoparticles of magnetite Fe₃O₄ and Fe synthesized by physical vapor deposition with a fast highly effective method using a solar energy have been studied. Targets have been prepared from tablets pressed from Fe₃O₄ or Fe powders. Relationships between the structure of nanoparticles and their magnetic properties have been investigated in order to understand principles of the control of the parameters of magnetic nanoparticles. Mössbauer investigations have revealed that the nanoparticles synthesized from tablets of both pure iron and Fe₃O₄ consist of two phases: pure iron and iron oxides (γ-Fe₂O₃ and Fe₃O₄). The high iron oxidability suggests that the synthesized nanoparticles have a core/shell structure, where the core is pure iron and the shell is an oxidized iron layer. Magnetite nanoparticles synthesized at a pressure of 80 Torr have the best parameters for hyperthermia due to their core/shell structure and core-to-shell volume ratio.     

Study on the synthesis of ε-Fe3N-based magnetic fluid

In this work, stable high-saturation magnetization ε-Fe₃N magnetic fluid was synthesized successfully by the chemical reaction of iron carbonyl (Fe(CO)₅) and ammonia gas (NH₃). The experiment results have shown that the reactive conditions, such as the nitriding temperature, the gas flux ratio of Ar1:Ar2:NH₃, the reactive time, the content of surfactant and the hole size of the porous plate used, have important effects on the phase composition, the size of magnetic particles, the magnetic properties and the stability of ε-Fe₃N magnetic fluid. Also it was found that the synthetic time of stable high saturation magnetization ε-Fe₃N magnetic fluid could be shortened by adding n-heptane into the carrier, and the size of ε-Fe₃N magnetic particles could be decreased by decreasing the pore size of the porous plate used in our experiment. Finally, stable ε-Fe₃N magnetic fluid with the saturation magnetization 1663 Gs and the mean particle size 12 nm was synthesized successfully.     

57Fe Mössbauer study of Fe nitrides

Summary Magnetic properties of Fe nitrides have been re-examined by⁵⁷Fe M?ssbauer spectroscopy. Hyperfine magnetic fields for α″-Fe₁₆N₂ are 30, 31 and 39T at 298K, but the averaged hyperfine field is 33T and nearly equal to the value of pure α-Fe. σ-Fe₂ N is an antiferromagnet below 9K having a small magnetic moment less than 0.1 μ_B, although γ′-Fe₄N and ε-Fe_3–2N are ferromagnets. ZnS-type FeN is non-magnetic at 4.2K. M?ssbauer spectra obtained from NaCl-type FeN are complex and some Fe atoms in this nitride show a surprisingly large hyperfine magnetic field of 49T. Paper presented at the ICAME-95, Rimini, 10–16 September 1995.     

Mössbauer studies of ɛ-Fe3−x Ni x N and γ′-Fe4−y Ni y N nanoparticles

Nanocrystalline ?-Fe_3?x Ni _x N (0.0?≤?×?≤?0.8) particles are synthesized by precursor technique and nitridation of decomposed products in NH₃ (g) in the temperature range 673 K-823 K. For x?=?0.1–0.4 compositions, single phase ?-Fe_3?x Ni _x N hexagonal structure with space group P6₃/mmc is formed, while for x?=?0.5–0.8, fcc γ′-Fe_4?y Ni _y N phase is also precipitated. The room temperature Mössbauer spectrum for all the compositions shows the presence of superparamagnetic doublet, which is attributed to ?-Fe_3?x Ni _x N phase. For x?=?0.5–0.8 compositions, two additional sextets are observed corresponding to two different iron sites, the corner position (Fe^c) and the fcc position (Fe^f), in γ′-Fe_4?y Ni _y N. The added Ni atoms preferentially substitute the corner Fe^c positions. The isomer shift, quadrupole splitting and hyperfine field values are found to change with the Ni content.     

The study of novel Fe3O4@γ-Fe2O3 core/shell nanomaterials with improved properties

The surface structure of the iron oxide nanoparticles obtained by the co-precipitation method has been investigated, and a thin layer of α-FeOOH absorbed on surface of the nanoparticle is confirmed by analyses of Fourier transform infrared (FTIR), X-ray photoelectron spectra (XPS) and surface photovoltage spectroscopy (SPS). After annealed at 400 °C, the α-FeOOH can be converted to γ-Fe₂O₃. The simple-annealed procedure resulted in the formation of Fe₃O₄@γ-Fe₂O₃ core/shell structure with improved stability and a higher magnetic saturation value, and also the simple method can be used to obtain core/shell structure in other similar system.     

Preparation and chemical stability of iron-nitride-coated iron microparticles

Iron-nitride-coated iron microparticles were prepared by nitridation of the surface of iron microparticles with ammonia gas at a temperature of 510 °C. The phases, composition, morphology, magnetic properties, and chemical stability of the particles were studied. The phases were α-Fe, ε-Fe₃N, and γ-Fe₄N. The composition varied from the core to the surface, with 99.8 wt% Fe in the core, and 93.8 wt% Fe and 6 wt% N in the iron-nitride coating. The thickness of the iron-nitride coating was about 0.28 μm. The chemical stability of the microparticles was greatly improved, especially the corrosion resistance in corrosive aqueous media. The saturation magnetization and the coercive force were 17.1×10³ and 68 kA/m, respectively. It can be concluded that iron-nitride-coated iron microparticles will be very useful in many fields, such as water-based magnetorheological fluids and polishing fluids.     

X-ray diffraction and Mössbauer Studies of γ′-(Fe1−xSnx)4N compounds (0.0⩽x⩽0.3)

The structure and magnetic properties of γ′-(Fe_1−xSn_x)₄N samples have been studied using X-ray diffraction and ⁵⁷Fe Mössbauer spectroscopy. It has been shown that the single-phase (Fe_1−xSn_x)₄N compounds can be prepared in the composition range of 0.0⩽x⩽0.3, which have the similar structure as γ′-Fe₄N The lattice parameter with the increase of Sn concentration can be well fitted with two linear relationships a₀(x)=3.795+0.019x (with x⩽0.10 ) and a₀(x)=3.797+0.228(x−0.10) (with 0.1⩽x⩽ 0.3). The fitting results of Mössbauer spectra indicate that the hyperfine parameters have the same changing tendency with lattice parameter, and the Sn atoms have a preference to be located at the corner site.     

Facile synthesis of flower-like α-Fe2O3/ZnFe2O4 architectures with self-assembled core-shell nanorods for superior TEA detection

Uniform flower-like α-Fe₂O₃ architectures with self-assembled core-shell nanorods are constructed and successfully prepared via the facile process. The concentration of Fe salt plays a great significance for morphological evolution from nanorods to self-assembled microflowers. Flower-like α-Fe₂O₃/ZnFe₂O₄ consisting of α-Fe₂O₃ core and ZnFe₂O₄ shell nanorods are derived from FeOOH/ZIF-8 precursors. The detailed studies reveal that the tunable growth of ZIF-8 nanoparticles on three-dimensional FeOOH microflowers at room temperature and the availble calcination regulation are responsible for the formation of core-shell Fe₂O₃/ZnFe₂O₄ composites. The highest response value of flower-like α-Fe₂O₃/ZnFe₂O₄ architectures to 100 ppm triethylamine (TEA) has been improved to 141 at 280 °C, which is calculated to be 6.2 times compared with flower-like α-Fe₂O₃ architectures (22.7). The enhanced gas-sensing mechanism of α-Fe₂O₃/ZnFe₂O₄ composites can be attributed to the typical microflowers structures, the large specific surface area, the effective heterojunctions between α-Fe₂O₃ core and ZnFe₂O₄ shell, and the improved electron transfer process.     

Characterization of iron nitrides prepared by spark erosion,plasma nitriding,and plasma immersion ion implantation

The effect of the nitrogen uptake in α-iron upon spark erosion in gaseous and liquid ammonia, plasma nitriding, and plasma immersion ion implantation is studied. The resulting phases and hyperfine parameters, measured by the Mössbauer spectroscopy, are discussed from the point of view of initial conditions of their preparation and subsequent heat and/or mechanical treatment. Spark erosion in the ammonia gas produces fine particles with the dominating ferromagnetic α-Fe phase (50%). The 20% of specimen volume form α′-Fe and α′′-Fe₁₆N₂ phases. The last 30% occupy the γ′-Fe₄N, ferro- and paramagnetic ε phases, and γ-Fe(N). Nitriding in the liquid ammonia allows to incorporate the higher content of nitrogen into α-iron particles which results in the formation of paramagnetic ε(ζ)-Fe₂N phase. This phase also dominates the surface of α-iron specimen implanted by nitrogen using plasma immersion ion implantation at 300°C/3 h, where high uptake of nitrogen (approx. 30 at%) is reached. Plasma nitriding at 510°C results in the formation of γ′-Fe₄N phase.     

Mössbauer studies of ultrafine particles of NiO and α-Fe2O3

Ultrafine particles of antiferromagnetic NiO and ferromagnetic -Fe₂O₃, supported on a high area silica material, were studied with the Mössbauer effect. The superferromagnetic transition was observed as a function of particle size and temperature. From the temperature variation of the Mössbauer spectra, magnetic anisotropy constants and particle size distributions were determined. Small particles of -Fe₂O₃ show increasing quadrupole splitting as the particle size is decreased. This effect is attributed to a large quadrupole splitting for the surface shell which has a different electric field gradient than the particle core. Analysis of the spectra using a simple surface shell model gives an estimate of the thickness and the electric field gradient of this shell. In contrast to bulk NiO, small particles of NiO show predominantly trivalent Fe hyperfine spectra over a wide temperature range. The stability of the trivalent iron may be due to a slight oxygen atom excess in the NiO lattice resulting in trivalent charge stabilization.     

Structural and Mössbauer studies of aerosol FeCu nanoparticles in a wide composition range

Structure and magnetic state of aerosol FeCu nanoparticles of 10–30 nm size with Cu content of 0.6–92.1 at.% have been examined by X-ray diffraction and Mössbauer spectroscopy. The FeCu particles have been shown to consist of an iron core surrounded by a copper and Fe oxide shell. With increasing Cu content the iron core having a bcc structure is reduced down to its complete disappearance followed by vanishing ferromagnetism of the particles. Within the copper content from 4.9 to 74.3 at.% the bcc and fcc phases coexist, with the fcc phase having a lattice constant close to that of pure copper and the bcc lattice constant being slightly higher than that for pure Fe due to embedding Cu atoms into the Fe lattice. At Fe-rich FeCu samples a presence of two-spin (ferromagnetic and paramagnetic) components of the fcc Fe is also observed. In the case of a thin copper shell there is only the ferromagnetic fcc Fe, whereas with further thickening of the shell both spin states of the fcc Fe appear existing up to a 20% Cu content. For FeCu samples with a higher Cu content they disappear due to oxidation of the copper grains. The Cu-rich samples with Cu content higher 80 at.% have a fcc structure, with the lattice constant being slightly higher than that of copper and they are paramagnetic. A slight increase of the lattice constant is due to the penetration of small iron aggregations into the Cu grains. In contact with air, the FeCu particles become covered with Fe₃O₄ and Cu₂O. Their long-term exposure to ambient conditions leads to further oxidation process of Cu₂O to CuO.     

Magnetic relaxation in nanocrystalline iron-oxides

Nanocrystalline Fe oxides are compacted solids of fine particles. By compacting interfaces are formed between adjacent particles. Since collective magnetic relaxation and superparamagnetism depend on the anisotropic energy, it is expected that the existence of interfaces and related interface anisotropy will change the relaxation behavior of nanocrystalline Fe oxides. Measurements on nanocrystalline α-Fe₂O₃ and γ-Fe₂O₃ have shown that the exchange interaction in the interfaces is more effective in suppressing superparamagnetic relaxation upon compacting than the dipole interaction.     

Amphiphilic Core–Shell Nanocomposite Particles for Enhanced Magnetic Resonance Imaging

A scalable synthesis of magnetic core–shell nanocomposite particles, acting as a novel class of magnetic resonance (MR) contrast agents, has been developed. Each nanocomposite particle consists of a biocompatible chitosan shell and a poly(methyl methacrylate) (PMMA) core where multiple aggregated γ‐Fe₂O₃ nanoparticles are confined within the hydrophobic core. Properties of the nanocomposite particles including their chemical structure, particle size, size distribution, and morphology, as well as crystallinity of the magnetic nanoparticles and magnetic properties were systematically characterized. Their potential application as an MR contrast agent has been evaluated. Results show that the nanocomposite particles have good stability in biological media and very low cytotoxicity in both L929 mouse fibroblasts (normal cells) and HeLa cells (cervical cancer cells). They also exhibited excellent MR imaging performance with a T₂ relaxivity of up to 364 mM_Fe^?1 s^?1. An in vivo MR test performed on a naked mouse bearing breast tumor indicates that the nanocomposite particles can localize in both normal liver and tumor tissues. These results suggest that the magnetic core–shell nanocomposite particles are an efficient, inexpensive and safe T₂‐weighted MR contrast agent for both liver and tumor MR imaging in cancer therapy.     

Nickel-induced magnetic behaviour of nano-structured α-Fe2O3, synthesised by facile wet chemical route

We report the synthesis of pristine and nickel containing iron oxide (α-Fe₂O₃) nanocrystallites by facile environmentally benign wet chemical process. The magnetic behaviour of the samples has been found to change progressively with nickel content. The Mössbauer spectra revealed the precipitation of secondary phase of nickel ferrite (NiFe₂O₄) at ～2?wt% nickel contents. The transmission electron micrographs together with asymmetric magnetic hysteresis loop have confirmed the formation of core–shell structure. The Morin temperature of nanostructured α-Fe₂O₃ as estimated by superconducting quantum interference device has been found to be 257, 245, 247 and 242?K at nickel content of 0, 1, 2 and 4?wt%, respectively. The similar trends of increase/decrease in Morin temperature have been noticed by Mössbauer analysis. Furthermore, below Morin temperature, the temperature range of coexisted antiferromagnetic and ferromagnetic states has been found to increase with increase in nickel content.     

Investigation of structure and magnetic properties of the as-deposited and post-annealed iron nitride films by reactive facing-target sputtering

Structure and magnetic properties of the as-deposited and post-annealed iron nitride films have been investigated systematically. A series of phases containing α-Fe, ?-Fe₃N, ξ-Fe₂N and γ″-FeN were obtained as nitrogen flow rate (FN₂) increases from 0.5 to 30 sccm. An increase of the nitrogen concentration in the as-deposited films could be concluded from the phase transition with the increasing FN₂. After being annealed, some of the iron nitride phases are decomposed and γ′-Fe₄N appears in the films. The magnetic characteristics are dependent on FN₂, which can be ascribed to the facts that the nitrogen in the films turns the valence states of Fe into Fe⁺ or Fe^dipole with high magnetic momentum or ever H-like bond Fe^+/dipole with low magnetic momentum based on the bond-band-barrier correlation mechanism.     

57Fe-Mössbauer parameters of iron tellurides at high temperatures

⁵⁷Fe Mössbauer spectroscopic studies on the β-Fe_1.12Te, δ′-Fe_1.33Te₂ and ε-FeTe_2.11 samples have been performed in the temperature range from room temperature to 1000K. The isomer shifts of β-Fe_1.12Te, δ′-Fe_1.33Te₂ and ε-FeTe_2.11 samples at 823K are 0.09, 0.18 and 0.17 mm/s, respectively. The smaller isomer shift of β-phase with iron in tetrahedral sites than those of δ′- and ε-phases with iron in octahedral sites may be explained probably due to small shielding by d-electrons. The effects of temperature and composition on the isomer shift and quadrupole splitting are discussed.     

Magnetic impedance of structured film meanders in the presence of magnetic micro- and nanoparticles

The magnetic impedance (MI) of film elements in the form of meanders with a [Fe19Ni81]/Cu]₄/Fe19Ni81/Cu/[Fe19Ni81/Cu]₄/Fe19Ni81 layered structure and variable geometry is studied. For the best meanders (having a maximal MI of up to 125% and an MI maximal sensitivity of about 30%/Oe), the influence of stray magnetic fields is determined. The stray fields are produced by spherical iron particles 500 μm in diameter and ferrofluids containing iron oxide nanoparticles. The feasibility of detecting intricately configured stray fields from a set of ferromagnetic spheres arranged on the surface of an MI element is demonstrated. The sensitivity of film meander MI elements to nonuniform external magnetic fields is simulated. The results of this work may be helpful in developing special-purpose magnetic sensors intended for micropositioning, nondestructive testing, and biomagnetic detection.