Ab initio, crystal field and experimental spectroscopic studies of pure and Ni-doped KZnF3 crystals

Pure and Ni²⁺ doped KZnF₃ single crystals were studied using the combination of the DFT-based ab initio methods, crystal field theory and experimental spectroscopic techniques. The electronic, optical and elastic properties have been calculated and compared with available experimental data and good agreement was achieved. Elastic anisotropy of pure KZnF₃ was modeled; calculations of the sound velocity, Debye temperature, Grüneisen parameter and specific heat capacity were performed. Comparison of the calculated results for the pure and doped material, which is reported for the first time for the considered material, enabled to identify the changes in the optical and electronic properties, which are due to the introduced nickel impurity ions. In particular, it was shown that the lowest Ni 3d states appear in the host's band gap at about 1.0 eV above the valence band. The changes of the electron density distribution after doping were also shown. Microscopic analysis of the crystal field effects based on the performed ab initio calculations of the Ni²⁺ density of states at different external pressures enabled to estimate the constants of the electron–vibrational interaction, Huang-Rhys factor, Stokes shift and local bulk modulus around impurity ions. The crystal field calculations of the Ni²⁺ energy levels were performed to analyze and assign the experimental absorption spectrum. Such a combination of the ab initio and semi-empirical calculating techniques leads to a complementary picture of the physical properties of KZnF₃:Ni²⁺ and can be applied to other doped crystals.     

Bright room-temperature green luminescence from YSZ:Tb

The room temperature spectroscopic properties of terbium doped zirconia fibres grown by Laser Floating Zone method are reported. The fibres were found to be stabilised in the tetragonal crystalline phase as measured by X-ray diffraction and Raman spectroscopy techniques. The doping with terbium ions was performed during the growth process and their incorporation on the wide band gap oxide host assumes an important role on the stabilisation of the high temperature tetragonal crystalline phase. Under ultraviolet optical pumping a bright green luminescence was observed by naked eye at room temperature, corresponding to the 4f → 4f transitions between the crystal-field split energy levels of the ⁵D₄ and ⁷F₅ manifolds of the 4f⁸ electronic configuration of the Tb³⁺ ions. These results suggest that YSZ:Tb³⁺ could be considered as a promising candidate for applications in green electroluminescent devices.     

Application of CLTD’s for High Resolution Mass Identification and for Stopping Power Measurements of Heavy Ions

An array of calorimetric low temperature detectors (CLTD’s) for energy sensitive detection of heavy ions was combined with time-of-flight (TOF) detectors to obtain a detector system for high resolution mass identification of low energy heavy ions. In addition the same setup was used to prove the ability of CLTD’s to be used in electronic stopping power measurements for heavy ions in matter. Experiments with 50?MeV ⁶³Cu and ⁶⁵Cu ions at the tandem accelerator at the MPI at Heidelberg, and with 25 to 250?MeV ²³⁸U ions at the UNILAC accelerator at GSI at Darmstadt have been performed. For ^63,65Cu at 50?MeV a mass resolution of Δm(FWHM)=0.9?amu, and for ²³⁸U in an energy range of 65 to 150?MeV a resolution of Δm(FWHM)=1.28?amu, was obtained. The results for stopping powers of ²³⁸U in carbon and gold are presented and compared with theoretical predictions and data from the literature.     

The influence of columnar defects on the critical current density in (Bi,Pb)2Sr2Ca2Cu3O10 + δAg tapes

An excellent tool to enhance the critical current density in superconductors is the controlled introduction of defects by irradiation damage. Irradiation with 2.65 GeV Au ions provides the generation of amorphous line defects. Polycrystalline (Bi, Pb)₂Sr₂Ca₂Cu₃O_{10 + δ} Ag tapes processed by the powder-in-tube technique were irradiated up to doses of 3.5× 10¹¹ Au ions/cm² at a temperature of 100 K. On the one hand, our irradiation experiments were performed to investigate the degree ofj _c enhancement and, on the other hand, to examine the flux pinning mechanism in (Bi, Pb)₂Sr₂Ca₂Cu₃O_{10 + δ} tapes. Characterization of the samples was performed by magnetization measurements using a vibrating sample magnetometer (VSM) up to 13 T in a temperature range between 5 and 100 K. Further, we have measured the relaxation of the magnetic moment before and after irradiation to determine the influence of columnar defects on the activation energyU. A comparison of the irradiation-induced effects with previous results obtained on Bi₂Sr₂CaCu₂O_{8 + δ} irradiation experiments is included.     

Detecting singly charged ions during field evaporation of tantalum at high temperatures

The field evaporation of tantalum from point emitters in a broad range of temperatures from T = 300 to 2500 K was studied using a static magnetic mass spectrometer equipped with a special field ion source. The room-temperature mass spectrum of field-evaporated particles displayed only the peaks of triply charged ions (Ta³⁺). As the temperature was increased, the charge of field-evaporated ions exhibited a decrease: at T ～ 1000 K, the peaks of doubly charged ions (Ta²⁺) prevailed. The peaks of singly charged ions (Ta⁺) were detected for the first time at temperatures in the interval 1900 K < T < 2500 K. The rate of evaporation of singly charged tantalum ions was several orders of magnitude lower than that of doubly charged ions.     

Copper(II) ion removal from aqueous solutions using biosorption technology: thermodynamic and SEM–EDX studies

The present study uses biosorption technology to remove copper(II) ions from aqueous solutions. Mature leaves of neem (Azadirachta indica) were developed into powder form of size 32–45 μm and used as the biosorbent, while copper(II) ion solutions were prepared to be used as adsorbates. Parameters varied include copper(II) ion concentration and adsorption temperature. The neem leaf powder (NLP) dosage which was kept constant at 1.0 g L^?1 and pH was between 5 and 6. Adsorption occurred at a high rate initially and reached equilibrium after 50 min. Adsorption seemed to be more favourable at higher temperatures. Optimal temperature was found to be 333 K, with a high adsorption capacity of 146.30 mg g^?1. Thermodynamic studies showed that the system is spontaneous and endothermic in nature, based on the parameters of Gibbs free energy (?G°), biosorption enthalpy (?H°) and biosorption entropy (?S°) obtained, which gave values of ?2.74, 26.70 and 0.07 kJ mol^?1 K^?1, respectively. The adsorption mechanism was found to be predominantly chemisorption. SEM and EDX results show that copper(II) ions were adsorbed on the micropores of NLP. Results indicate that NLP is a suitable biosorbent for removing copper(II) ions from solutions.     

Structural,electrical and magnetic properties of polycrystalline La0.67(Ca1−x Sr x )0.33MnO3 manganites

Polycrystalline La_0.67(Ca_1?x Sr _x )_0.33MnO₃ with different substitution level of strontium element, were synthesized via solid state reaction. Structure of samples was characterized by X-ray diffraction (XRD). XRD patterns reveal that La_0.67Ca_0.33MnO₃ exhibits orthorhombic structure with space group Pnma. Phase transitions from orthorhombic to rhombohedral take place as Ca ions were gradually substituted by Sr ions. The XRD data were further analyzed by Rietveld refinement technique. The data show that Mn–O–Mn bond angle increases as x increases. Microstructures obtained from SEM show that substitution of Sr ions has demoted the grain growth and densification process during sintering. The substitution of Sr ions has greatly influenced the hopping integral of electron via double exchange interaction, thus affecting the electrical properties and magnetic properties as well. The resistivity decreases and the metal–insulator transition temperature (T _p ) shifts to higher temperature as x increases. The magnetoresistance (MR) effect gradually decreases and MR peak shifts to higher temperature as x increases. The magnetization measured at room temperature is found to be increasing as x increases.     

Luminescent properties of vanadium-doped SnO2 nanoparticles

This paper reports the influence of doping degree and annealing temperature on XRD, Raman, EPR and PL spectra of Sn_1−xV_xO₂ nanoparticles with x = 0, 0.01 and 0.05 annealed at 600 and 800 °C. XRD studies reveal a tetragonal rutile crystalline phases of tin oxide, while the formation of V₂O₅ secondary phase was evidenced for all doped nanoparticles only by Raman scattering. In function of the doping degree and annealing temperature, from EPR spectroscopy was evidenced the presence of three different positions for V⁴⁺ ions in the samples: isolated ions disposed on the nanoparticles surface, ions which are coupled by dipolar or exchange interactions and cluster ions. The luminescence emissions associated with oxygen vacancies and structural defects are influenced by doping degree and annealing temperature and could be correlated with the crystallite size determined from XRD patterns.     

Structural and magnetic characterization of LiMn1.825Cr0.175O4 spinel obtained by ultrasonic spray pyrolysis

Quaternary spinel oxide LiMn_1.825Cr_0.175O₄ powder was synthesized by using an ultrasonic spray pyrolysis method, without additional annealing. The crystal structure of the as-prepared powder was revealed by X-ray powder diffraction and identified as a single spinel phase with Fd3m space group. The powders had a spherical morphology with extremely smooth surface appearance and densely congested interior structure. Transmission electron microscopy confirmed that the particle consisted by the cohesion of the primary particles. Magnetic measurements performed in DC field in both zero-field-cooled and field-cooled regimes, as well as AC susceptibility experiments, show that system undergoes spin-glass transition at the freezing temperature T_f = 20 K. The value of the effective magnetic moment μ_eff = 4.34 μ_B obtained from the Curie-Weiss fit in the high temperature region confirms the substitution of Mn³⁺ ions with Cr³⁺ ions.     

Ferromagnetic Behavior of Fe+ Implanted Si(100) Semiconductor

Fe ions have been implanted into Si (100) single crystals using ion implantation technique. The Fe ions have been accelerated to 45 keV with a dose of 5×10¹⁷ ion/cm² at room temperature. The ions have been sent to the substrate??s surface at normal incidence. The temperature dependence of magnetization measurement was explored at the temperature range of 10?C300 K. The implanted Si substrate was studied with Ferromagnetic Resonance (FMR) technique and Vibrating Sample Magnetometer (VSM). The FMR spectra were recorded by applying external magnetic field in different experimental geometries. FMR spectra were analyzed and the magnetic properties, which are the g-factor, effective magnetization and uniaxial anisotropy parameter, were estimated by simulation of the experimental data. The sample showed two-fold magnetic anisotropic symmetry. By fitting the Si-2p region obtained through XPS measurements it is observed that Fe and Fe compounds are present in the material.     

Effects of Co content and annealing temperature on the structure and optical properties of CoxMg1−xAl2O4 nanoparticles

Co_xMg_1−xAl₂O₄ (x = 0–0.8) nanoparticles were synthesized by sol–gel method, and characterized by X-ray powder diffraction and transmission electron microscopy. X-ray photoelectron spectroscopy and ²⁷Al solid-state NMR spectroscopy were performed to study the chemical environments of cations in the nanoparticles as a function of cobalt content and annealing temperature. The results show that the crystallite size of the particles is about 20–40 nm. Besides the tetrahedral and octahedral coordinations, the second octahedrally coordinated Al³⁺ ions are observed in the samples. The inversion parameter (two times the fraction of Al³⁺ ions in tetrahedral sites) decreases with the increase of annealing temperature and cobalt content. The fraction of octahedral Mg²⁺ decreases with the increase of Co concentration. The absorption spectra indicate that Co²⁺ ions are located in the tetrahedral sites as well as in the octahedral sites in the nanoparticles. The intensity of the absorption peak corresponding to octahedral Co²⁺ ions (300–500 nm) decreases with increasing annealing temperature.     

Effect of Ce Doping on the Magnetic Properties of NiFe2O4 Nanoparticles

In the present work, effect of different concentration of Ce ions on the magnetic properties of nickel ferrite nanoparticles is discussed. A series of NiCe _x Fe_2?x O₄ (x=0.0–0.10) samples were prepared by a chemical route. XRD patterns show that all the samples are in pure spinel phase except that with x=0.10. This indicates that rare earth ions have limited solubility in the spinel lattice. Magnetic properties are studied by electron paramagnetic resonance spectroscopy (EPR) and the results are explained in terms of a magnetic moment obtained by a vibrating sample magnetometer. Mössbauer spectroscopy was performed to have an idea about the distribution of ions between the tetrahedral and octahedral sites. Magnetic moment is found to decrease after doping with Ce ions. It was found that the samples show mixed spinel nature rather than the pure inverse character. Doping with Ce ions reduces the EPR linewidth of pure nickel ferrite, which indicates that eddy current losses are reduced.     

EPR and optical absorption studies of Cr3+ ions in alkaline earth alumino borate glasses

Electron paramagnetic resonance (EPR) and optical absorption spectra of Cr³⁺ ions in Calcium alumino borate (CaAB) glasses have been studied. The EPR spectra exhibit weak resonance signal at g ≈ 4.50 and intense resonance signal at g ≈ 1.98. A sharp resonance signal at g ≈ 1.97 was also observed at lower concentrations of chromium. The concentration dependence of the linewidth of the resonance signal at g ≈ 1.98 suggests the formation of Cr³⁺ ion clusters by magnetic superexchange interactions. The temperature dependence of the peak to peak intensity and the linewidth of the resonance signal at g ≈ 1.98 suggests that the exchange interactions between Cr³⁺ ions in the present sample were antiferromagnetic in nature with Néel temperature, T _N = 233 K. From the number of spins participating in the resonance at g ≈ 1.98, the paramagnetic susceptibility (χ) was calculated at different temperatures (233–295 K). A plot of 1/χ and T was found to obey Curie-Weiss law with negative Curie temperature. By measuring the relative intensities of the resonance signal at g ≈ 1.98, at different temperatures, the value of antiferromagnetic coupling constant (J) has been estimated. The optical absorption spectrum of chromium doped CaAB glass exhibits four bands, characteristic of Cr³⁺ ions, in nearly octahedral symmetry. From the band positions, the crystal field splitting parameter, Dq and the Racah interelectronic repulsion parameters, B and C were evaluated. The optical band gap (E_opt) and the Urbach energy (ΔE) were calculated from the ultraviolet absorption edges.     

Study of magnetic inhomogeneity in β-Cu3Fe4V6O24

The temperature dependence of dc magnetization and electron paramagnetic resonance (EPR) spectra of the ??-Cu₃Fe₄V₆O₂₄ multicomponent vanadate were investigated. Dc magnetic measurements showed the presence of strong antiferromagnetic interactions (Curie-Weiss temperature, ?? ?? 80 K) at high temperatures, while zero-field-cooled (ZFC) magnetization revealed a cusp-like maximum in low fields at T _f1 = 4.4 K, which coincides with the splitting of the ZFC and FC curves. Another maximum was registered at T _f2 = 3.0 K. These two temperatures (T _f1 and T _f2) could be regarded as freezing temperatures in the spin glass state of two magnetic sublattices of Fe1 and Fe2 ions. The EPR spectrum of ??-Cu₃Fe₄V₆O₂₄ is dominated by a nearly symmetrical, very intense and broad resonance line centered at g _eff ?? 2.0 that could be attributed to iron ions. Below 10 K, an additional EPR spectrum with g ₁ = 2.018(1) and g ₂ = 2.175(1) appears, as well as a very weak line at g_eff = 1.99(1). The former spectrum is probably is due to divalent copper ions, and the latter line due to vanadium V⁴⁺ complexes. The temperature dependence of EPR parameters (g-factor, linewidth, integrated intensity) was determined in the range of 3?C300 K. Two low-temperature maxima in the temperature dependence of the integrated intensity (at 40 and 6 K) were fitted with a function suitable for pairs of exchange-coupled Fe³⁺ ions. A comparison of dc magnetic susceptibility and EPR integrated intensity indicates the presence of spin clusters, which play an important role in determining the low-temperature magnetic response of _??-Cu₃Fe₄V₆O₂₄.     

Synthesis of magnetite nanoparticles by thermal decomposition of ferrous oxalate dihydrate

Two different polymorphs of ferrous oxalate dihydrate were synthesized by precipitation of ferrous ions with oxalic acid: α-Fe(C₂O₄) · 2H₂O with a monoclinic unit cell is obtained after precipitation and ageing at 90 °C, whereas the orthorhombic β-type is formed after precipitation at room temperature. The morphology of the oxalate crystals can be tailored from prismatic crystals of the α-polymorph over star-like aggregates of α/β-mixtures to non-agglomerated crystallites of β-oxalate. Thermal decomposition in air gives hematite at T ≥ 250 °C; if the thermolysis reaction is performed at low oxygen partial pressures (e.g., T = 500 °C and p _O2 = 10^?25 atm) magnetite is obtained. The synthesized magnetite is stoichiometric as signaled by lattice parameters of a ₀ = 8.39 Å. The thermal decomposition of ferrous oxalate is monitored by thermal analysis, XRD, and IR-spectroscopy. The morphology of the oxalate crystals is preserved during thermal decomposition; the oxalates are transformed into spinel particle aggregates of similar size and shape. The crystallite size of the magnetite particles increases with temperature and is 40 or 55 nm, if synthesized from β-oxalate at 500 °C or 700 °C, respectively. The saturation magnetization of the magnetite particles decreases with decreasing particle size. Since the particles are larger than the critical diameter for superparamagnetic behavior they display hysteresis behavior at room temperature.     

Fracture mechanical properties in controlled rolled CMn thermomechanically treated steels with splittings

Fracture mechanical properties of a thermomechanically treated CMn steel were investigated in both longitudinal and transverse directions relative to the rolling direction. The CTOD fracture toughness testing was performed at three deformation rates in the temperature range from −60 to +40°C. Fracture initiation was investigated at room temperature. The CTOD fracture toughness depended very much on the specimen orientation with respect to sulphide inclusions. In the transverse specimens, maximum load was reached just after yielding, hence the recorded CTOD_m values were nearly independent of the rate of deformation and testing temperature.     

Spin Gap Effects on Bulk R1+x ba2−x Cu3O7−δ (R=Eu or Nd and 0≤x≤0.4)

Spin gap effects on the underdoping states of the bulk system of R_1+x Ba_2?x Cu₃O_7?δ (R = Eu or Nd and 0 ≤ x ≤ 0.4) were investigated through transport property measurements. The underdoping states were achieved by, alternatively substituting R³⁺ for Ba²⁺ ions in the system rather than adjusting the oxygen deficiency. The excess R³⁺ ions were to occupy the Ba sites of the crystalline lattice as revealed from Rietveld analysis for powder X-ray diffraction. The underdoped materials were observed to first undergo spin pairing transition in the temperature range well above T _c, and come across with superconducting transition at T _c. The increasing feature observed for spin gap temperature and the decreasing one for T _c, as the concentration of holes decreases, are in qualitatively good agreement with theoretical predictions from the mean-field RVB model.     

Synthesis, Structural and Magnetic Properties of Polypyrrole Coated Ni0.2Ca0.8Fe2O4 Nanocomposite

The nanoparticles of spinel ferrites having composition Ni_0.2Ca_0.8Fe₂O₄ were synthesized by an advanced sol-gel method and subsequently coated with intrinsically conducting polypyrrole (PPy) by chemical oxidative polymerization of the corresponding monomer (pyrrole) using ammonium peroxodisulphate as oxidant. The X-ray diffraction and TEM measurements were obtained to understand the crystalline structure, size and morphology of evolution of the samples. The dc electrical investigation revealed that at room temperature the surface conductivity increased from 2.8×10^?5 S?cm^?1 to 1.5×10^?3 S?cm^?1 on polymerization. M?ssbauer investigations revealed that the polymerization causes migration of Fe³⁺ ions from A to B site, resulting to the enhancement of the observed hyperfine field. In agreement with this, the dc magnetization measurements performed on VSM revealed an enhancement in saturation magnetization in the M?CH curves on polymerization. The value of blocking temperature (T _B) is found to have credibly increased from 110 K to 130 K, which confirms the increase in crystallite size after polymerization.     

Interdiffusion and phase formation at room temperature in evaporated gold-tin films

Interdiffusion at room temperature in evaporated Au-Sn films was studied by the in situ backscattering of 2.0 MeV ⁴He ions. The interdiffusion resulted in the formation and growth of an AuSn phase region. The growth of the phase followed a parabolic growth rate law, and the growth rate constant was found to be about 9 × 10^?15 cm²s^?1 at room temperature.     

The investigation of Zn content on the structure and electrical properties of Zn x Cu0.2Ni0.66Mn2.14?x O4 negative temperature coefficient ceramics

The effects of Zn content on the structure and electrical properties of Cu–Ni–Mn–O based negative temperature coefficient thermistors were investigated. Series of Zn _x Cu_0.2Ni_0.66Mn_2.14?x O₄ (0?≤?x?≤?1) ceramics were prepared by Pechini method. Cu2p_3/2 X-ray photoelectron spectra demonstrate that Cu⁺ and Cu²⁺ ions at A sites decrease with increase of x, and all the Cu ions exist as Cu²⁺ (B) at x of 1.0 due to the almost exclusive occupation of Zn ions at A sites. X-Ray diffraction spectra show that a single cubic spinel structure is formed at a low Zn content (x?≤?0.6), and NiO and CuO start to appear at x of 0.8. The segregation of NiO at x?≥?0.8 is caused by the migration of Cu ions for A to B sites. With Zn content x increasing from 0 to 1.0, the electrical resistivity increases from 42 to 980?Ω?cm which can be attributed to the decrease of the electrical conduction caused by Cu ions at A sites. The resistivity drift decreases sharply from 12.6 to 4.2% with increasing x from 0 to 0.4, and the value is only 0.16% at x of 1.0.