CEMS studies of structural modifications of metallic glasses by ion bombardment

Fe₇₆Mo₈Cu₁B₁₅ and Fe₇₄Nb₃Cu₁Si₁₆B₆ amorphous metallic alloys were exposed to ion bombardment with nitrogen ions and protons to ensure different degree of radiation damage. The radiation damage profiles were calculated in the “full cascade” mode. Conversion electron Mössbauer spectrometry was employed to scan structural modifications in the surface regions of the irradiated alloys. In Fe₇₆Mo₈Cu₁B₁₅, the irradiation with 130 keV N⁺ has caused a significant increase of the hyperfine magnetic fields and isomer shift due to changes in topological and chemical short-range order (SRO), respectively. No appreciable effects were revealed after bombardment with 80 keV H⁺ ions. Fe₇₄Nb₃Cu₁Si₁₆B₆ amorphous metallic alloy was irradiated by 110 keV N⁺ and 37 keV H⁺ and only changes in chemical SRO were revealed after bombardment with nitrogen ions. The observed alternations of the structure depend primarily on the total number of displacements of the resonant atoms which are closely related to the fluence as well as type and energy of the incident ions.     

Study of the oxidation kinetics of vanadium carbide

The oxidation of an oxycarbide of vanadium, VO_0.6C_0.7, and of a vanadium carbide, VC_0.98, was studied athermally up to temperatures of 800° C and isothermally between 400 and 580° C at oxygen pressures ranging from 10^–2 to 1 atm. The oxycarbide followed the parabolic rate law below 450° C with V₂O₅ forming as the only reaction product. The activation energy was 49 kcal/mole. VC_0.98 did not form an oxide in this temperature range, but rather dissolved oxygen, the activation energy being 26.6 kcal/mole. No oxygen pressure dependence on the kinetics was found for either sample in this temperature range. Both samples followed the cubic rate law during oxidation in the range of 500–580° C during which V₂O₅ formed. There was a P^1/3 dependence and the activation energy was the same for both materials, 51 kcal/mole. The cubic rate law and the positive pressure dependency (rather than an anticipated negative dependency) were attributed to an electric field associated with oxygen ions chemisorbed on a thin layer of V₂O₅.     

Corrosion behaviour of zirconium electrode in sodium azide electrolyte as compared to the alkali halide solutions

The kinetics of open circuit growth of an oxide film on zirconium electrode in NaN₃ solution of various concentrations was investigated using potential and capacitance measurements. The protective oxide film formed in azide solutions was found to thicken with time in two steps, the rate of oxide growth was found to decrease as the azide concentration increased. The corrosion behaviour of the electrode was characterized by ac impedance measurements to obtain detailed information about the effect of azide ion concentration on the electrical properties of the Zr electrode surface. The impedance response for the metal‐metal oxide‐electrolyte system was modeled with a transfer function. The potentiodynamic oxidation of Zr was also studied as a function of the azide ion concentration. The polarization curves showed the peak‐shaped active‐to‐passive transition and the corrosion rate was found to increase with increase of azide ion concentration. The activation energy of corrosion was calculated according to Arrhenius plot and found to be 14.5 kJ mol^?1. The polarization results in azide solutions were compared to those obtained in solutions of different halide ions, namely, F^?, Cl^?, Br^? and I^? ions. The rate of corrosion was found to decrease in the order Br^? > Cl^? > F^?, I^? > azide. Opposite to the behaviour in azide solutions, the halide ions do not show the active‐passive transition.     

Ion energy and mass distributions of the plasma during modulated pulse power magnetron sputtering

Modulated pulse power (MPP) sputtering is a variation of high power pulsed magnetron sputtering (HPPMS) that overcomes the rate loss issue and achieves enhanced plasma ionization through modulation of the pulse shape, intensity, and duration. In this study, the principle and characteristics of MPP/HPPMS technique are first introduced. An electrostatic quadrupole plasma mass spectrometer installed parallel to the target surface has been used to examine the plasma properties, including time averaged ion energy and mass distributions of the positive ions, generated during sputtering a metal Cr target in pure Ar and Ar/N₂ atmospheres using MPP and continuous dc power sources in a closed field unbalanced magnetron sputtering system. It was found that the MPP plasma exhibits a low ion energy peak at 1-2 eV and a short ion energy tail with the maximum ion energy affected by the peak current and power utilized on the cathode. A significantly increased numbers of single and double charged Cr and Ar ions were identified in the MPP plasma as compared to the dc plasma in pure Ar. The number of ions (ion flux) increased when the peak target power and current were increased. Besides single and double charged Cr, Ar and N ions, N₃⁺, N₄⁺, CrN⁺ and CrN₂⁺ ion species were also identified in the MPP discharge with the introduction of N₂ into the system. The ion energy distributions of ion species for the MPP plasma in Ar/N₂ atmosphere exhibit similar peak values and tail distributions to those of the MPP plasma in pure Ar atmosphere. However, the energy tail extended toward higher energies due to the increased peak current and power on the cathode as the N₂ flow rate percentage was increased in the system.     

Crystallization mechanism of Fe78Si13B9 amorphous alloy induced by ion bombardment

The crystallization behavior of Fe₇₈Si₁₃B₉ amorphous alloys induced by Ar ion bombardment was investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis. The crystallization process of amorphous alloys can be controlled by adjustment of ion incident angles (θ), beam density and substrate temperature. The compressive stress caused by ion bombardment will result in the decrease of critical nucleation energy and induce the crystallization of amorphous alloy even at very low temperature, and the thermal effect converted from energetic ions will improve the crystallization of amorphous alloys. The crystallization process of amorphous alloy induced by ion bombardment was a stress induced phase transformation process assisted by thermal effect.     

Color-tunable and white-light emitting lanthanide complexes based on (CexEuyTb1−x−y)2(BDC)3(H2O)4

Ce³⁺, Eu³⁺ and Tb³⁺ complexes were synthesized through facile and mild approaches with terephthalic acid (H₂BDC) as the ligand. Their chemical compositions were determined as (Ce_xEu_yTb_1−x−y)₂(BDC)₃(H₂O)₄ by elemental analysis (EA), Fourier transform infrared (FTIR) spectra and X-ray diffraction (XRD) measurements. Fluorescent properties of the as-synthesized complexes were investigated by changing the molar ratio of Ce³⁺, Tb³⁺ and Eu³⁺ ions, and the optimized ratio of 3.0:2.0:0.15 for Ce³⁺:Tb³⁺:Eu³⁺ in the complex was determined for white-light emission. Tuning on the emitting color was realized by adjusting the ratio among lanthanide ions, indicating the energy transfer process inside the complex. It was found that Tb³⁺ could sensitize the fluorescence of Eu³⁺ while its own fluorescence was quenched by the latter ion, and concentration quenching of Ce³⁺ was also observed. Fairly good thermal stability and oxidation resistance of the as-synthesized complexes were also demonstrated.     

Spectroscopic and crystal-field analysis of energy levels of Eu in SnO2 in comparison with ZrO2 and TiO2

We have carried out systematic crystal-field energy level calculations of Eu³⁺ ions doped in SnO₂ based on experimentally acquired luminescence spectra. In addition, with an aim of revealing systematic trends in spectra and crystal-field effects for Eu³⁺ ion in similar hosts, we have analyzed the TiO₂ (anatase):Eu³⁺ spectra as well. The obtained crystal-field parameters yield very good agreement between the calculated and observed energy levels. Emphasis has been put on analysis of the crystal-field-induced J-mixing effects and their roles in getting proper sets of crystal-field parameters and energy levels. A more general theory concerning J-mixing effects has been proposed and the relevant results will be valuable to understanding of the spectral characteristics of Eu³⁺ f-f transition spectra in other hosts. Relations between the maximum crystal-field splitting of some selected J-manifolds with J = 1 and J = 2 and crystal-field invariants have been re-visited and re-derived. The corresponding numbers of crystal-field parameters influencing the splitting of these manifolds have been taken into account in every case. The derived equations have been tested in applications to three systems (SnO₂, TiO₂ (three sites) and ZrO₂). Consistent results have been obtained, which confirms validity of the performed crystal-field analysis and opens a way for possible applications of the suggested calculating technique to other rare-earth ions.     

Enhancement of electrical conductivity of polypyrrole film by stretching: Counter ion effect

The effect of counter ions on the structure and properties of polypyrrole films was investigated. Various aliphatic and aromatic sulfonates as well as some typical inorganic ions such as BF₄⁻, ClO₄⁻and PF₆⁻ were employed as the counter ions. The films were prepared by anodic oxidation of pyrrole in propylene carbonate containing tetraethylammonium salt of the corresponding counter ion and 1 vol.% of water at −20 °C. The electrical conductivity and elongation of the films were highly dependent upon the structure of the counter ions. Among the counter ions investigated, PF₆⁻ gave a film with the highest conductivity (4.0 × 10² S/cm) and elongation (135%). The film stretched up to 2.5 times its original length showed a conductivity of 1.6 × 10³ S/cm in the stretch direction. A linear relationship was observed between the d-spacing measured by X-ray diffraction and the size of the counter ion. Films with smaller counter ions, both unstretched and stretched, showed higher conductivity, although the anisotropy in conductivity of the stretched films was independent of the size of the counter ion.     

The structure and properties of chromium nitride coatings deposited using dc, pulsed dc and modulated pulse power magnetron sputtering

The time averaged ion energy distributions and ion fluxes of continuous dc magnetron sputtering (dcMS), middle frequency pulsed dc magnetron sputtering (PMS), and modulated pulse power (MPP) magnetron sputtering plasmas were compared during sputtering of a Cr target in an Ar/N₂ atmosphere in a closed field unbalanced magnetron sputtering system. The results showed that the dcMS plasma exhibited a low ion energy and ion flux; the PMS plasma generated a moderate ion flux of multiple high ion energy regions; while the MPP plasma exhibited a significantly increased number of target Cr⁺ and gas ions with a low ion energy as compared to the dcMS and PMS plasmas. Cubic CrN coatings were deposited using these three techniques with a floating substrate bias. The structure and properties of the coatings were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, nanoindentation, microscratch and ball-on-disk wear tests. It was found that the deposition rate of the MPP CrN depositions was slightly lower than those of the dcMS depositions, but higher than in the PMS depositions at similar average target powers. The coatings deposited in the dcMS and PMS conditions without the aid of the substrate bias exhibited large columnar grains with clear grain boundaries. On the other hand, the interruption of the large columnar grain growth accompanied with the renucleation and growth of the grains was revealed in the MPP CrN coatings. The MPP CrN coatings exhibited a dense microstructure, fine grain size and smooth surface with high hardness (24.5 and 26 GPa), improved wear resistance (COF = 0.33 and 0.36) and adhesion, which are the results of the low ion energy and high ion flux bombardment from the MPP plasma.     

Synthesis and electrochemical characteristics of Fe-P alloy prepared by electrothermal reduction method

Microscale Fe-P alloy was prepared using Ca₃(PO₄)₂ and Fe₂O₃ in an electrothermal reduction process, and the electrochemical performance was investigated in detail. The initial discharge capacity could reach ∼566.8 mAh/g at 0.3 C rate, and the fade trend was so slight that the normalized capacities from 1.0 to 2.0 C rate were adjacent. The energy density and the power density could reach ∼1133.6 Wh/kg and ∼912.4 W/kg, respectively. The rate capability and the cycle performance were comparable to those of the Fe-P alloy synthesized using zerovalent iron and phosphorus. At 0.5 mV/s scan rate, the oxidation peak and the reduction peak for the reaction of lithium ions with P were positioned at ∼1.3 and ∼0.5 V, respectively. The reaction occurred under diffusion control, and the lithium ion diffusion efficient was ∼1.5×10⁻⁹ cm²/s.     

Evolution of structural and optical properties in the course of thermal evolution of sol-gel derived cobalt-doped gahnite

Thermal evolution of sol-gel derived gahnite (ZnAl₂O₄) with 4, 8 and 12 at.% of Zn replaced with Co was studied by thermal analysis techniques (DTA/TGA), X-ray diffraction (XRD) and UV-vis diffuse reflectance spectroscopy (DRS). Zinc-cobalt spinel powders were produced by gel heat treatment at temperatures as low as 400 °C. Crystal structure was characterized using Rietveld refinement of X-ray diffraction patterns for the samples annealed at 800 °C, simultaneously with the analysis of diffraction line broadening. It was found out that the distribution of Co²⁺ ions in tetrahedral and octahedral sites of zinc cobalt aluminate crystal lattice, crystallite size and lattice strain depend on Co loading. The green color of samples thermally treated at T < 800 °C has been explained as a consequence of partial oxidation of Co²⁺ ions at lower temperatures and accommodation of Co³⁺ ions in octahedral sites. Thermal treatment at higher temperatures promote gradual change of color from green to blue, characteristic for tetrahedrally coordinated Co²⁺ ions. The spectra evolution could be interpreted as a progressive reduction of Co³⁺ to Co²⁺ ions at higher temperatures.     

Thermal, structural and magnetic properties of some zinc phosphate glasses doped with manganese ions

(MnO)_x·(P₂O₅)₄₀·(ZnO)_60−x glasses containing different concentrations of MnO ranging from 0 to 20 mol% were prepared by the melt-quenching technique. The samples had a fixed P₂O₅ content of 40 mol% and the MnO:ZnO ratio was varied. The thermal, structural and magnetic properties of these glasses were investigated by means of differential thermal analysis (DTA), electron paramagnetic resonance (EPR) and magnetic susceptibility measurements. Compositional dependence of the glass transition (T_g), crystallization (T_p) and melting temperatures were determined by DTA investigations. From the dependence of the T_g on the heating rate (a), the activation energy of the glass transition (E_g) was calculated. The fragility index (F) for the studied glasses was determined to see whether these materials are obtained from kinetically strong-glass-forming (KS) or kinetically fragile-glass forming (KF) liquids. The EPR spectra of the studied glasses revealed absorptions centered at g ≈ 2.0, 3.3 and 4.3. The compositional variations of the intensity and line width of these absorption lines was interpreted in terms of the variation in the concentration of the Mn²⁺ and Mn³⁺ ions in the glass and the interaction between the manganese ions. EPR and magnetic susceptibility data reveal that both Mn²⁺ and Mn³⁺ ions are present in the studied glasses, their relative concentration being dependent on the glass composition. Magnetic susceptibility data reveal an antiferromagnetic interaction between the manganese ions for the glasses containing 20 mol% MnO.     

Zinc treatment effects on corrosion behavior of Alloy 600 in high temperature, hydrogenated water

Trace levels of soluble zinc(II) ions (30 ppb) maintained in mildly alkaline, hydrogenated water at 260 °C were found to reduce the corrosion rate of Alloy 600 (UNS N06600) by about 40% relative to a non-zinc baseline test [S.E. Ziemniak, M. Hanson, Corros. Sci., in press, doi:10.1016/j.corsci.2005.01.006]. Characterizations of the corrosion oxide layer via SEM/TEM and grazing incidence X-ray diffraction confirmed the presence of a chromite-rich oxide phase and recrystallized nickel. The oxide crystals had an approximate surface density of 3500 μm⁻² and an average size of 11 ± 5 nm. Application of X-ray photoelectron spectroscopy with argon ion milling, followed by target factor analyses, permitted speciated composition versus depth profiles to be obtained. Numerical integration of the profiles revealed that: (1) alloy oxidation occurred non-selectively and (2) zinc(II) ions were incorporated into the chromite-rich spinel: (Zn_0.55Ni_0.3Fe_0.15)(Fe_0.25Cr_0.75)₂O₄. Spinel stoichiometry places the trivalent ion composition in the single phase oxide region, consistent with the absence of the usual outer, ferrite-rich solvus layer. By comparison with compositions of the chromite-rich spinel obtained in the non-zinc baseline test, it is hypothesized that zinc(II) ion incorporation was controlled by the equilibrium for

0.55Zn²⁺(aq)+(Ni_0.7Fe_0.3)(Fe_0.3Cr_0.7)₂O₄(s)?0.40Ni²⁺(aq)+0.15Fe²⁺(aq)+(Zn_0.55Ni_0.3Fe_0.15)(Fe_0.3Cr_0.7)₂O₄(s)     

Structural characterization of layered LiNi0.85−xMnxCo0.15O2 with x = 0, 0.1, 0.2 and 0.4 oxide electrodes for Li batteries

We report the synthesis of LiNi_0.85−xCo_0.15Mn_xO₂ positive electrode materials from Ni_0.85−xCo_0.15Mn_x(OH)₂ and Li₂CO₃. XRD and XPS are used to study the effect of Mn-doping on the microstructures and oxidation states of the LiNi_0.85−xCo_0.15Mn_xO₂ materials. The analysis shows that Mn-doping promotes the formation of a single phase. With increasing substitution of Mn ions for Ni ions, the lattice parameter a decreases, while the lattice parameters c and c/a increase. XPS revealed that the oxidation states of Ni, Co and Mn in LiNi_0.85−xCo_0.15Mn_xO₂ compounds (where x = 0.1, 0.2 and 0.4) were +2/+3, +3 and +4. The substitution of Mn ions for Ni ions induces a decrease in the average oxidation state of Ni. Because the substitution of Mn for Ni ions is complex, the extent of the changes between the lattice parameter and L_M-O differ. The occupation of Ni in Li sites is affected by the ordering of Mn⁴⁺ with Ni²⁺ and Mn⁴⁺ with Li⁺.     

Structural studies on iron-tellurite glasses prepared by sol-gel method

In this study, we report structural properties of the iron-tellurite glasses obtained using the sol-gel synthesis. The samples were characterized by X-ray diffraction, FTIR, UV-vis and EPR spectroscopy. Our results indicate dominant presence of iron ions in the trivalent state and the existence some Fe²⁺ ions. The analysis of the IR spectra indicates a gradual transformation of iron ions from tetrahedral into octahedral sites when the concentration of Fe(NO₃)₃ is increased beyond 0.64 mol%. EPR studies show that the increase of Fe(NO₃)₃ content in the host matrix induces the growth of the number of effective g values. This can be explained considering that the orbitals of O²⁻ ion with a large spin-orbit interaction constant will interact with the 3d orbital of Fe³⁺ ion bonded to this O²⁻ ion, thus leading to appearance of an orbital angular momentum which contributes to the magnetic moment of Fe³⁺ ion. A strong dipolar interaction, which is more predominant in a glass with higher content of Fe(NO₃)₃, causing a localized magnetic field along the site of the Fe³⁺ ions and the increase the effective g values.     

Morphology influence of the oxidation kinetics of carbon nanofibers

This paper reports the stability and oxidation rate of five types of carbon nanofiber (CNF) with distinctly different orientation of their graphite sheets based on conversion to CO₂ when heated in the presence of oxygen. A non-isothermal technique was used to determine the oxidation kinetic parameters including the activation energy (E_a). Graphite shows a similar activation energy (E_a = 158 kJ/mol⁻¹) to CNF with longitudinal alignment (E_a = 156 kJ/mol⁻¹). CNF type herringbone (E_a = 126 kJ/mol⁻¹) and platelet (E_a = 145 kJ/mol⁻¹) show the lowest oxidation resistance which improved dramatically after a heat treatment at 3023 K of the herringbone (E_a = 216 kJ/mol⁻¹) and platelet (E_a = 174 kJ/mol⁻¹) structures.     

Oxidation of Ni-base alloys in atmospheres with widely varying oxygen partial pressures

The oxidation behavior of the Ni-base alloys IN 617, IN 713 LC, Ni20Cr, and Ni20Cr+Si has been investigated in the temperature range from 850°C to 1000°C in air and at low-oxygen partial pressure p(O₂) (10^–19 to 10^–16 bar). With the exception of alloy IN 713 LC, the materials show no influence of p(O₂) on the oxidation mechanisms and the kinetics. This result can be explained by the formation of a dense Cr₂O₃ layer, the growth rate of which is controlled by the Cr ion interstitial concentration in Cr₂O₃ at the phase boundary oxide/alloy and the mobility of Cr ions in Cr₂O₃. For the alloy IN 713 LC which develops a dense Al₂O₃ layer in air, a modified transition mechanism at low p(O₂) leads to the formation of Cr₂O₃ at the surface and a strong internal oxidation of Al.     

Surface modification of Zr-based bulk amorphous alloys by using ion irradiation

Surfaces of the [Zr_0.65Cu_0.18Ni_0.09Al_0.08]₉₈M₂ (M = Er and Gd) bulk amorphous alloys were modified by irradiation with energetic singly charged argon (Ar⁺) ions. Samples of both the alloys were irradiated with 2.17 × 10¹⁷ argon ions of 10 keV energy. As cast and ion irradiated samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Mechanical properties like Vicker's hardness, nanohardness, elastic modulus and elastic recovery were measured. Considerable increase in elastic modulus and hardness was observed because of ion irradiation in these alloys. The ion irradiated samples of the [Zr_0.65Cu_0.18Ni_0.09Al_0.08]₉₈Er₂ alloy showed better properties as compared to [Zr_0.65Cu_0.18Ni_0.09Al_0.08]₉₈Gd₂ alloy. CuZr₂ phase was detected in ion irradiated alloys by XRD and confirmed by EDS. The range of Ar⁺ ions was found to be approximately 9.3 ± 5.4 nm in both alloys.     

Effect of oxygen partial pressure on the high-temperature oxidation of CVD SiC

The oxidation behavior of chemically vapor-deposited silicon carbide (CVD SiC) was studied at 1670-2010 K in O₂-Ar and CO₂-Ar. The oxidation kinetics in O₂-Ar was parabolic or linear parabolic, and was parabolic in CO₂-Ar. The activation energy for the parabolic rate constants (k_p) was 210-220 kJ/mol in O₂-Ar, and was 290-300 kJ/mol in CO₂-Ar. The oxygen partial pressure (P_O2) dependence of k_p was expressed as k_p∝ (P_O2)ⁿ, where n=0.08-0.13 and 0.37-0.53 in O₂-Ar and CO₂-Ar, respectively. Bubbles were formed at more than 1985 K and P_O2>5 kPa. The bubble formation temperature decreased with decreasing P_O2 at P_O2<5 kPa.     

Structural, dielectric and magnetic properties of Nd-doped Co2Z-type hexaferrites

Z-type hexaferrites doped with Nd³⁺, Ba_3−xNd_xCo₂Fe₂₄O₄₁ (x = 0, 0.05, 0.10, 0.15, and 0.25), were prepared by solid-state reaction. The effect of the Nd³⁺ ions substitution for Ba²⁺ ions on the microstructure and electromagnetic properties of the samples was investigated. The results reveal that an important modification of microstructure, complex permeability, complex permittivity, and static magnetic properties can be obtained by introducing a relatively small amount of Nd³⁺ instead of Ba²⁺. SEM image shows that the grains of the ferrites doped with Nd³⁺ were smaller, more perfect and homogeneous than that of the pure ferrite. The real part (?′) of complex permittivity and imaginary part (?″) increase at first, and then decrease with increasing Nd content. At low frequency, the imaginary part μ″ of complex permeability decreases with Nd content and then increases when frequency is above 7.0 GHz. The magnetization (M_s) and the coercivity (H_c) are 79.38 emu g⁻¹ and 36.94 Oe for Ba_2.75Nd_0.25Co₂Fe₂₄O₄₁. The data of magnetism show that the ferrite doped with Nd³⁺ ions is a better soft magnetic material due to the higher magnetization and lower coercivity.