Magnetotransport in core-shell Fe–Fe oxide nanostructures

Magnetic and magnetotransport measurements were performed on gas-phase synthesized Fe nanoparticles subjected to surface oxidation and cold consolidation. Two samples were investigated with α-Fe volume fraction of 0.15 and 0.60. The sample with smaller metallic fraction is below the percolation threshold for metallic conduction and the conduction mechanism is dominated by thermally activated processes across the oxide. In this case, by lowering the temperature, an increase of the negative magnetoresistance is observed up to 5% at 50 K in a magnetic field of 70 kOe. The magnetoresistance dependence on the sample magnetization, temperature and sample composition is discussed considering the magnetic correlations present in these nanostrucuterd systems.     

High-purity Zirconium under Niobium ion implantation: possibility of a dynamic precipitation?

High-purity (6N purity) Zirconium was subjected to different Niobium ion (Nb⁺) fluences in a particle accelerator. Grazing incidence X-ray diffraction confirmed subsurface phase transformation. While an approximate scaling was noted between Nb⁺ fluence and quantum of phase transformation, the sample subjected to the highest ion irradiation also showed significant subsurface shear residual stresses (τ₁₃). Molecular dynamics simulations, considering momentum transfer, revealed a drop in τ₁₃ beyond a critical displacements per atom or Nb⁺ fluence. High-resolution cross-sectional transmission electron microscopy (HRXTEM) confirmed formation of bcc (body-centred cubic) β phase and also linked τ₁₃ with such transformation. HRXTEM revealed, at about 100 nm depth, presence of 10–15% β with 2–15 nm size. The β particles and the surrounding α also had significant microscopic shear strains. The dynamic nature of the Nb implantation is expected to create fluctuations in temperature, Nb concentration and relative lattice damage. Such fluctuation, on the other hand, is/was hypothesized to dynamically alter the critical nuclei size: a clear possibility of ‘dynamic precipitation’.     

Mechanomaking of nanostructure in nitrided Fe–Cr alloys by cyclic “dissolution–precipitation” deformation-induced transformations

Structural-phase transformations in surface layers of iron and Fe? Cr? (Ni) alloys subjected to ion-plasma nitriding and subsequent cold plastic compression shear deformation in Bridgman anvils have been investigated by the methods of Mössbauer spectroscopy, transmission electron microscopy and X-ray analysis. It has been shown that the deformation-induced cyclic phase “dissolution–precipitation” transformations of nitrides in alloys lead to the formation of nitrogen oversaturated solid solutions, precipitation of secondary nitrides and nanostructurization of the metal matrix.     

Thermodynamic modeling of oxide phases in the Fe–Mn–O system

A critical evaluation and thermodynamic modeling for thermodynamic properties of all oxide phases and phase diagrams in the Fe–Mn–O system are presented. Optimized Gibbs energy parameters for the thermodynamic models of the oxide phases were obtained which reproduce all available and reliable experimental data within error limits from 298 K to above the liquidus temperatures at all compositions covering from known oxide phases, and oxygen partial pressure from metal saturation to 0.21 bar. The optimized thermodynamic properties and phase diagrams are believed to be the best estimates presently available. Two spinel phases (cubic and tetragonal) were modeled using Compound Energy Formalism (CEF) with the use of physically meaningful parameters. The present Fe–Mn spinel solutions can be integrated into a larger spinel solution database, which has been already developed. The database of the model parameters can be used along with a software for Gibbs energy minimization in order to calculate any type of phase diagram section and thermodynamic properties.     

Photoluminescence properties of Er-doped β-FeSi2 grown by ion implantation

Photoluminescence (PL) properties of Er-doped β-FeSi₂ (β-FeSi₂:Er) and Er-doped Si (Si:Er) grown by ion implantation were investigated. In PL measurements at 4.2 K, the β-FeSi₂:Er showed the 1.54 μm PL due to the intra-4f shell transition of ⁴I_13/2→⁴I_15/2 in Er³⁺ ions without a defect-related PL observed in Si:Er. In the dependence of the PL intensity on excitation photon flux density, the obtained optical excitation cross-section σ in β-FeSi₂:Er (σ=7×10⁻¹⁷ cm²) is smaller than that in Si:Er (σ=1×10^-15 cm²). In the time-resolved PL and the temperature dependence of the PL intensity, the 1.54 μm PL in β-FeSi₂:Er showed a longer lifetime and larger activation energies for non-radiative recombination (NR) processes than Si:Er. These results revealed that NR centers induced by ion implantation damage were suppressed in β-FeSi₂:Er, but the energy back transfer from Er³⁺ to β-FeSi₂ was larger than Si:Er.     

The effect of Cu on precipitation in Al–Mg–Si alloys

TEM investigations of two alloys isothermally heat treated at 175°C and 260°C show how Cu additions to the Al–Mg–Si system affect precipitation. Both alloys had a solute content Mg?+?Si?=?1.3 at.%, 0.127 at.% Cu, but with Mg/Si 0.8 and 1.25. Cu-containing Guinier-Preston (GP) zones and three types of Q′ precursors are identified as most common phases at peak-hardness conditions, whereas β″ accounts for maximum 30% of the total number of precipitates. The precursors have needle (L and S precipitates) or plate (C precipitate) morphologies. They consist of different arrangements of Al, Mg and Cu atoms on a grid defined by triangularly arranged Si planes parallel with and having the same period as {100} Al planes. The Si grid is composed of nearly hexagonal sub-cells of a?=?b?=?4.05?Å, c?=?4.05?Å. The Cu arrangement on the grid is often disordered in the needle precursors. The plate precursor is ordered, with a monoclinic unit cell of a?=?10.32?Å, b?=?8.1?Å, c?=?4.05?Å, γ?=?101°.     

The effect of Zn on precipitation in Al–Mg–Si alloys

Effects of addition of Zn (up to 1 wt%) on microstructure, precipitate structure and intergranular corrosion (IGC) in an Al–Mg–Si alloys were investigated. During ageing at 185?°C, the alloys showed modest increases in hardness as function of Zn content, corresponding to increased number densities of needle-shaped precipitates in the Al–Mg–Si alloy system. No precipitates of the Al–Zn–Mg alloy system were found. Using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), the Zn atoms were incorporated in the precipitate structures at different atomic sites with various atomic column occupancies. Zn atoms segregated along grain boundaries, forming continuous film. It correlates to high IGC susceptibility when Zn concentration is ~1wt% and the materials in peak-aged condition.     

The nitrogen-absorption isotherm for Fe–21.5 at. % Cr alloy: dependence of excess nitrogen uptake on precipitation morphology

Nitriding of Fe–21.5 at. % Cr alloy leads to a “discontinuously coarsened”, chromium-nitride/ferrite lamellar precipitation morphology in the nitrided zone. The nitrogen-absorption isotherm for this alloy with this precipitation morphology was determined at 560°C. To assure a constant precipitation morphology the Fe–21.5 at. % Cr specimen was first homogeneously pre-nitrided (at 580°C in an ammonia/hydrogen gas mixture of nitriding potential 0.103 atm^?1/2) and then de-nitrided (at 470°C in hydrogen gas atmosphere). The amount of nitrogen remaining in the de-nitrided specimen indicated that the composition of the nitride precipitates is CrN and not (Fe, Cr)N. The measured nitrogen-absorption isotherm revealed the presence of excess nitrogen in the nitrided specimen, which is a surprise in view of the coarse, lamellar precipitation morphology. The occurrence of this excess nitrogen could be ascribed to an unexpected, minor fraction of the total chromium content in the alloy present as coherent, tiny nitride platelets within the ferrite lamellae of the “discontinuously coarsened” lamellar precipitation morphology, as evidenced by transmission electron microscopy. A possible kinetic background for this unusual phenomenon was discussed.     

Positron annihilation study of ageing precipitation in deformed Fe–Cu–B–N–C

The role of deformation-induced defects and carbon addition on copper precipitation during ageing at 550?°C is investigated in high-purity Fe–Cu–B–N–C alloy samples by positron annihilation spectroscopy. Complementary small-angle neutron scattering (SANS) and hardness tests are utilized to characterize the size distribution of the Cu precipitates formed and their influence on the mechanical properties. Samples with 0 and 8% cold pre-strain are utilized to study the influence of prior tensile deformation on the precipitation kinetics of copper. The time evolution of the coincidence Doppler-broadening spectra indicates that deformation-induced defects enhance the Cu precipitation kinetics, which is confirmed by the SANS results. In the S–W plot, a clear reduction in open volume defects is accompanied by a strong increase of Cu signature during the initial stage of ageing, implying that the open volume defects (mainly dislocations) act as nucleation sites for Cu precipitation. A comparison between the precipitation behaviour of Fe–Cu, Fe–Cu–B–N and Fe–Cu–B–N–C indicates that the addition of carbon does not alter the Cu precipitation mechanism but decelerates the kinetics. Hardness results confirm that carbon counteracts the acceleration of Cu precipitation caused by the addition of B and N.     

The heat treatment response of semisolid formed Al–5Fe–4Cu alloy

The effect of heat treatment on both microstructures and performances of semisolid Al–5Fe–4Cu alloy was investigated with scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) and tensile test. The results showed that the semi-solid Al–5Fe–4Cu alloy’s response to the solution heat treatment (SHT) is abnormal compared with the conventional semi-solid Al alloys, i.e. the tensile properties of the semi-solid Al–5Fe–4Cu alloy decreased significantly after SHT. Nevertheless, the semi-solid Al–5Fe–4Cu alloy subject to direct ageing without SHT could exhibit conspicuous improvement of the tensile properties. And, the reason of the abnormal results has been analysed and discussed in detail.     

Synthesis of Ag metallic nanoparticles by 120 keV Ag− ion implantation in TiO2 matrix

TiO₂ thin film synthesized by the RF sputtering method has been implanted by 120 keV Ag^? ion with different doses (3?×?10¹⁴, 1?×?10¹⁵, 3?×?10¹⁵, 1?×?10¹⁶ and 3?×?10¹⁶ ions/cm²). Further, these were characterized by Rutherford back Scattering, XRD, X-ray photoelectron spectroscopy (XPS), UV–visible and fluorescence spectroscopy. Here we reported that after implantation, localized surface Plasmon resonance has been observed for the fluence 3?×?10¹⁶ ions/cm², which was due to the formation of silver nanoparticles. Ag is in metallic form in the matrix of TiO₂, which is very interestingly as oxidation of Ag was reported after implantation. Also, we have observed the interaction between nanoparticles of Ag and TiO₂, which results in an increasing intensity in lower charge states (Ti³⁺) of Ti. This interaction is supported by XPS and fluorescence spectroscopy, which can help improve photo catalysis and antibacterial properties.     

Enhancement in age hardenability of sintered Ti–5Fe alloy by Zr addition processed by pulsed electric current sintering

The age-hardenable Ti–5Fe–5Zr (wt. %, 5Zr) alloy has been consolidated by pulsed electric current sintering, following a β solution treatment, and the results are compared with a Ti–5Fe (0Zr) alloy. The precipitation sequence measured at 640°C ageing is β?+?athermal ω?→?β?+?isothermal ω?→?β?+?α. At the peak hardness isothermal ω phase forms at 20?s of ageing. The Zr addition retards the precipitation kinetics of the α phase; as a result, the α phase nucleates at latest at 300?s ageing in the overaged state. Fe is partitioned into β, while it is depleted from the α phases. There is Zr enrichment near the α/β interface when the α phase precipitates due to a solute drag effect; the growth rate of the α phase in the 5Zr alloy is significantly reduced compared with that in the 0Zr alloy.     

The effect of hardening by annealing in ultrafine-grained Al–0.4Zr alloy: influence of Zr microadditives

Influence of annealing on the microstructure and mechanical properties has been studied for Al–Zr (0.4 wt.%) alloy with the ultrafine-grained (UFG) structure formed by high-pressure torsion (HPT) at room temperature. A drastic hardening effect by short-term annealing in the temperature range of 90–280°С was observed for the HPT-processed Al–Zr alloy. The effect of hardening by annealing for the HPT-processed Al–Zr alloy is compared with that for the HPT-processed commercial purity (CP) Al. It was shown that addition of 0.4 wt.% Zr in Al does not cause a significant impact on the magnitude of hardening by annealing up to 150°С, however it leads to a shift of its maximum to higher annealing temperatures and expansion of the thermal stability range of strength up to 280°С. The kinetics of hardening by annealing for CP Al and Al–Zr alloys in the UFG state has been studied for the first time. It was shown that in both materials the strength first increases linearly with the duration of annealing and then reaches saturation. The temperature dependence of the rate of hardening by annealing was analysed through an Arrhenius law, and apparent activation energy was extracted for both systems. The addition of Zr results in the reduction of the activation energy of annealing-induced hardening by ～2 times. Possible physical mechanisms controlling the kinetics of hardening by annealing are discussed for the ultrafine-grained CP Al and Al–Zr alloy.     

Allotropic forms of carbon in the Invar Fe–Ni–C alloy before and after plastic deformation by upsetting

The effect of cold plastic deformation by upsetting (e = 1.13) on structure and hybridised bonds of carbon in the fcc Invar Fe-30.9%Ni-1.23% C alloy was studied by means of X-ray phase analysis and X-ray photoelectron spectroscopy. Carbon precipitates along grain boundaries and inside of grains in the alloy after annealing and plastic deformation were revealed. The presence of mainly sp²- and sp³-hybridised C–C bonds attributing to graphite and amorphous carbon as well as the carbon bonds with impurity atoms and metallic Fe and Ni atoms in austenitic phase were revealed in the annealed and deformed alloy. It was shown for the first time that plastic deformation of the alloy results in partial destruction of the graphite crystal structure, increasing the relative part of amorphous carbon, and redistribution of carbon between structural elements as well as in a solid solution of austenitic phase.     

Orientation magnetic phase transition induced by shock loading of the Fe–Cr–Co alloy

The strength characteristics of Fe–Cr–Co alloys have been investigated under high-strain-rate deformation of samples. It has been found that, under shock-wave loading, a significant remanent magnetization appears in the samples and their fragments due to the orientation magnetic phase transition. The threshold pressures of the magnetic phase transition have been determined, and the distribution of the remanent magnetization in the samples has been analyzed.     

The structure of a long-period stacking phase in an Mg–Al–Y alloy studied by electron microscopy

A new phase with a 10H-type long-period stacking (LPS) structure was found in an Mg₇₅Al₁₀Y₁₅ alloy annealed at 823?K. The LPS structure in the Mg₇₅Al₁₀Y₁₅ alloy annealed at 823?K for 2?h has an ordered arrangement of L1₂-type structural Al₆Y₈ clusters on the two-dimensional plane parallel to the c-plane of hexagonal Mg lattice and a disordered arrangement along the c-axis, whereas a perfectly ordered structure along the c-axis, which has a period with two times of that of the 10H-type LPS structure, was established by annealing at 823?K for 24?h. The structural model of the ordered LPS phase is proposed by high-resolution images taken with a Cs-corrected scanning transmission electron microscope and also electron diffraction patterns.     

Deformation-induced atomic redistribution in bcc Fe–Mn alloy

Deformation-induced iron and manganese atomic separation in a bcc solid solution is detected via Mössbauer spectroscopy in Fe_93.2Mn_6.8 alloy after high pressure torsion deformation in Bridgman anvils. The rate of short-range separation grows along with the temperature of deformation.     

The Haven ratio of Ag ion in α-AgI by Monte Carlo method

The temperature dependence of the Haven ratio of Ag ion in α-AgI is computed by a Monte Carlo method under the following assumptions: (1) Ag ions travel on the non-Bravais lattice points formed by 12(d) sites of bcc by I ions. (2) The pair interaction between two Ag ions consists of a Coulomb term. (3) A caterpillar mechanism is introduced in a proper way. It is confirmed that there exist the correlation in successive jump of ions in diffusion process even for a disordered crystal such as α-AgI. The Haven ratio derived from the present calculation is in good agreement with the experimental one.     

Thermal analysis of precipitation reactions in a Ti–25Nb–3Mo–3Zr–2Sn alloy

A study was undertaken on a Ti–25Nb–3Mo–3Zr–2Sn alloy using differential scanning calorimetry (DSC) in order to improve understanding of the precipitation reactions occurring during aging heat treatments. The investigation showed that isothermal ω phase can be formed in the cast and solution treated alloy at low aging temperatures. An exothermic peak in the temperature range of 300 to 400°C was detected for precipitation of the ω phase, with approximate activation energy of 176 kJ/mol. The ω phase begins to dissolve at temperatures around 400°C and precipitation of the α phase is favoured at higher temperatures between 400°C and 600°C. An exothermic peak with activation energy of 197 kJ/mol was measured for precipitation of the α phase. Deformation resulting in the formation of the stress induced α″ phase altered the DSC heating profile for the solution treated alloy. The exothermic peak associated with precipitation of the ω phase was not detected during heating of the deformed material and increased endothermic heating associated with recovery and recrystallisation was observed.     

Isolation of fe charge states by ion implantation and their study by mössbauer spectroscopy

Matrix isolation of impurity atoms in a frozen rare-gas lattice is a well-known technique for the study of atoms in quasi-free states. The usual procedure consists of co-evaporating these atoms together with the matrix atoms and depositing them simultaneously on a cold substrate. Subsequently, the frozen samples can be studied by optical spectroscopy or, as has been proved more recently, by Mössbauer spectroscopy.

The technical limitations of the co-evaporation procedure narrow the application range of this method. We have therefore tried to develop the ion implantation technique as a suitable alternative to the co-evaporation. Ion implantation does not put any limitation on the species and the concentration of the isolated atoms; moreover, it is particularly suited for the isolation of radioactive impurities, which may be investigated by Mossbauer spectroscopy.

In a first series of experiments, we have implanted ⁵⁷Co into a frozen Xe matrix, hereby producing isolated Fe⁺ and Fe⁰ states by the electron capture decay of the implanted nuclei.¹ A second experiment was devoted to the study of ⁵⁷Fe implanted in solid O₂.² Due to the high reactivity of oxygen, it would have been impossible to produce this sample by co-evaoporation. Mössbauer data show some evidence that in this case Fe⁶⁺ states have been produced. The results of these experiments will be discussed and further perspectives will be sketched.