Role of copper ions in dielectric and structural investigations of lead– borate glasses

Glasses in the system 0.1CuO-(x-0.1)PbO-(1-x)B₂O₃ (0.3≤ x ≤ 0.7) were synthesized by using the melt quench technique. A number of studies such as X-ray diffraction (XRD), differential scanning calorimetry (DSC), fourier-transform infrared (FTIR) and Raman spectroscopy, electron paramagnetic resonance (EPR) and dielectric properties (viz., dielectric constant ??, dielectric loss and ac conductivity σ_ac) are employed to characterize the glasses. The amorphous nature of the glasses was confirmed using XRD while the glass transition temperature (T_g) of glass samples have been estimated from DSC investigation and found that the T_g decreases with increasing PbO content. Raman and FTIR spectroscopy reveals that when increasing lead ions, the tetrahedral [BO₄] units are gradually replaced by trigonal [BO₃] units. The EPR study leads to determine the local site of Cu²⁺ ions and its transformation with the Pb content in the studied glasses.     

CW EPR, echo-detected EPR, and field-step ELDOR study of molecular motions of nitroxides ino-terphenyl glass: Dynamical transition, dynamical heterogeneity and β-relaxation

Continuous-wave electron paramagnetic resonance (CW EPR), echo-detected (ED) EPR, and field-step electron-electron double resonance (FS ELDOR) were simultaneously applied to study molecular motions of nitroxide spin probes of two different types in glassyo-terphenyl. A strong linear temperature dependence of the overall splitting of the CW EPR lineshape was found for nitroxide Tempone and only a weak one for a phenyl-ring-containing imidasoline nitroxide. The linear temperature dependence of the splitting is explained within the model of harmonic librations. The assessed libration frequency for Tempone is of the order of 3·10¹² rad/s. The observed remarkable difference between the two nitroxides is explained by the different strength of interactions between guest and host molecules and by dynamical heterogeneity of the glass. The nonlinear temperature dependence above 250 K is attributed to the onset of anharmonic motion that is postulated in a number of neutron scattering and Mössbauer spectroscopy studies for molecular glasses and proteins (the so-called dynamical transition). Above 245 K also ED EPR spectra change drastically, which may be explained on the same ground. Magnetization transfer was observed in FS ELDOR for nitroxide Tempone, with a time constant around 10^?5 s. It was found to be almost temperature-independent between 160 K and 265 K and was attributed to the Johari-Goldstein β-relaxation process. For the phenyl-ring-containing imidasoline nitroxide this transfer was not observed, which may be explained again by the dynamical heterogeneity of the glass and by small effectivity of the β-relaxation process in this case.     

A statistical model for ESR line shape of lithium colloids created by γ irradiation in HLi

Electron paramagnetic resonance results of small lithium particles created in lithium hydride by γ irradiations are presented. The EPR line was found to be inhomogeneous and the spin lattice relaxation time for conduction electrons to be unusually large (10^?4?10^?6s). We point out that the EPR line width is induced by the dispersion of the total nuclear magnetic moment inside the small particle. We assume that the size distribution of lithium particles created by γ irradiation is a logarithmiconormal distribution. Different experimental results confirm this model.     

Strontium Tetraborate Glasses Doped with Transition Metal Ions: EPR and Optical Absorption Study

Electron paramagnetic resonance (EPR) and optical studies have been carried out on Cu(II)-, VO(II)- and Cr(III)-doped strontium tetraborate glasses to understand the distortion and substitution of these ions. The EPR results of Cu(II) glass indicate that g _∥ > g _⊥, typical for the tetragonally elongated octahedral site of the Cu(II) impurity. The evaluated covalency parameter 0.788 suggests a moderate covalency for the bonding. By correlating EPR and optical results, the in-plane π-bonding β₁ ² is evaluated as 0.715. In the vanadium-doped glasses, the distortion must be a tetragonally elongated octahedron, similar to Cu(II). However, the EPR studies show that g _⊥ > g _∥ indicating the tetragonally compressed octahedral site for the ion. The site symmetry is C _4V. Supported by the optical absorption, evaluated parameters propose a moderate covalency. The EPR and optical results for Cr(III) glass indicate the distorted octahedral site symmetry in the host lattice. These results further suggest that the bonding between Cr(III) and the ligands is covalent. Authors' address: Renduchintala V. S. S. N. Ravikumar, Department of Physics, Acharya Nagarjuna University, Nagarjuna Nagar 522510, India     

Short-range order changes induced by heat treatment in yttrium-aluminosilicate glasses

Short-range order and local atomic configuration in yttrium-aluminosilicate glasses doped with gadolinium were studied by infrared (IR) spectroscopy, ²⁷Al magic-angle-spinning nuclear magnetic resonance (MAS-NMR) and Gd³⁺ electron spin resonance (EPR) on as-prepared and heat-treated samples.A small amount of yttrium was replaced by gadolinium in the host glass because Y³⁺ and Gd³⁺ cations are quite similar and gadolinium ions can be used as structural sensor in electron paramagnetic resonance measurements. The results evidence weak changes in the structure of as-prepared glasses with respect to the coordination of aluminium atoms produced by gadolinium doping (0.2 and 0.5 mol%). New IR bands recorded from heat-treated samples are associated with stretching modes of hexacoordinated aluminium in AlO₆ octahedra. The effect of the heat treatment on aluminium environment is estimated by analysing the relative intensity of the component lines of simulated ²⁷Al MAS-NMR spectra. High-coordinated AlO_n species were identified in all samples. EPR results evidence the increase of the number of gadolinium sites with weak crystal field as effect of the structural relaxation.     

A Study of Mechanochemical Doping of Fluoride Crystals with a Fluorite Structure by Er3+ Ions via Electron Paramagnetic Resonance Spectra

Using electron paramagnetic resonance (EPR) spectroscopy, we have shown that, upon mecha- noactivated doping of powders of compounds CaF₂, SrF₂, and BaF₂ with Er³⁺ ions, impurity centers of single erbium ions with cubic symmetry are formed. Investigations of dependences of EPR spectra intensities on the particle size show that the process of mechanochemical doping with Er³⁺ ions proceeds differently for CaF₂, SrF₂, and BaF₂ host matrices. In the case of CaF₂, impurity centers are localized in a very thin near-surface layer of CaF₂ particles, in SrF₂, the impurity is distributed over the volume of particles, while, in BaF₂, there is a layer of a finite thickness for which the probability of doping in the course of mechanosynthesis is very small and the impurity of the rare-earth element is localized in the core of large particles. These data can be explained assuming that the result of mechanosynthesis of particles of fluorides with a fluorite structure doped with Er3+ ions at room temperature is governed by two processes—mechanoactivated diffusion of rare-earth ions into particles and segregation of impurity ions at grain boundaries. In this case, the typical scales for compounds CaF₂, SrF₂, and BaF₂ considerably differ from each other.     

Structure of New Bis-Dicarbollyl Derivatives of Transition Metals

The dipyridyl complexes of the copper salts of bis-o-dicarbollyliron(III), -cobalt(III), and -nickel(III) are investigated by means of EPR spectroscopy. Theoretical models of the EPR spectra of copper(II) ions in these complexes are constructed and their spectral parameters are determined. It is shown that in all cases the tetragonally distorted octahedron is the most probable coordination sphere of the Cu²⁺ ions.     

EPR characterization of organic free radicals in marine diesel

The intensive unresolved central line associated with organic free radicals in electron paramagnetic resonance (EPR) spectra of petroleum is interpreted as resulting from the superposition of signals from different radical species with very close g values. The mobility of a free radical in crude oil is relatively low due to the high oil viscosity. Aimed at characterizing free radicals in the oil byproduct, the present study is concerned with the investigation of marine diesel (bunker), a low-viscosity oil. Marine diesel was studied by EPR spectroscopy at X-band (9 GHz) in the temperature range from 170 to 400 K. Despite the viscosity at room temperature (2.5·10⁻³ kg/m·s) and the tumbling correlation time for free radicals of about 10⁻⁷ s suggesting a high mobility of free radicals in marine diesel, the EPR spectra at room temperature did not exhibit resolved lines, but only an envelope with a poor signal-to-noise ratio. The same behavior was observed from 170 to 373 K. Above 373 K, the EPR spectrum exhibited resolved lines: a superposition of a septet-quartet, a sextet-quartet and a quintet-quartet group of lines was identified with the following parameters: g = 2.003 ± 0.001, proton hyperfine couplings A = 6.41 ± 0.03 G (septet) and A′ = 1.82 ± 0.02 G (quartet); g = 2.003 ± 0.001, A = 6.21 ± 0.03 G (sextet) and A′ = 1.64 ± 0.02 G (quartet); g = 2.003 ± 0.001, A = 6.16 ± 0.03 G (quintet) and A′ = 1.83 ± 0.02 G (quartet), which were attributed to phenalenyl radicals and their derivatives. Below 373 K, phenalenyl dimerization prevented its detection by EPR.     

Electron paramagnetic resonance of scandium in silicon carbide

The EPR spectra of scandium acceptors and Sc²⁺(3d) ions are observed in 6H-SiC crystals containing a scandium impurity. The EPR spectra of scandium acceptors are characterized by comparatively small hyperfine interaction constants, whose values are consistent with the constants for other group III elements in SiC: boron, aluminum, and gallium acceptors. The EPR spectra of scandium acceptors undergo major changes in the temperature interval 20–30 K. In the low-temperature phase the EPR spectra are characterized by orthorhombic symmetry, whereas the high-temperature phase has higher axial symmetry. The EPR spectra observed at temperatures above 35 K and ascribed by the authors to Sc²⁺(3d) ions, or to the A ²⁻ state of scandium, have significantly larger hyperfine structure constants and narrower lines in comparison with the EPR spectra of scandium acceptors. The parameters of these EPR spectra are close to those of Sc²⁺(3d) in ionic crystals and ZnS, whereas the parameters of the EPR spectra of scandium acceptors correspond more closely to the parameters of holes localized at group III atoms, in particular, at scandium atoms in GeO₂. It is concluded that in all centers the scandium atoms occupy silicon sites. Fiz. Tverd. Tela (St. Petersburg) 39, 52–57 (January 1997)     

EPR and UV spectrometry investigation of sucrose irradiated with carbon particles

Solid state/EPR (SS/EPR) dosimeters of carbon ions irradiated sucrose are studied with EPR, and their water solutions – with UV spectroscopy. Doses between 20 and 200 Gy are used with linear energy transfer (LET) values for carbon ions of 63, 77, 96 and 230 keV μm^?1. After irradiation all samples show typical for irradiated sucrose EPR and UV spectra. The obtained data are compared with those previously reported for nitrogen particles and gamma rays irradiated sucrose. The identical shape of both the EPR and UV spectra of irradiated with various type radiation samples suggests that generated free radicals are not influenced by the nature of radiation. The lack of difference in the line width of the separate lines or the whole EPR spectrum, obtained for gamma and heavy particles irradiation, suggests negligible spin–spin interaction among the radiation-generated free radicals in the samples. The linear dependence of the EPR response on the absorbed dose radiation is found to be higher when generated by gamma rays, than by the same absorbed dose of heavy particles. In addition, the EPR response for carbon ions is higher than that for nitrogen ions. Water solutions of irradiated sucrose exhibit UV spectrum with absorption maximum at 267 nm, attributed to the recombination products of free radicals. The UV band intensity depends on the absorbed dose radiation. The UV spectra obtained for carbon, nitrogen and gamma rays irradiated sucrose are also compared.     

Quantitative EPR spectroscopy: Comparison between primary standards and application to MgO-MnO and α-Al2O3-Cr2O3 solid solutions

To study their reliability as primary standards in the quantitative EPR spectroscopy, a large series of pure paramagnetic compounds with known spin concentrations, whose spectra vary considerably in intensity, shape, structure and overall width are compared. The paramagnetic species examined as pure solid compounds and solutions, were free radicals (DPPH and TEMPO), vanadyl and Cu²⁺ ions (S = 1/2), Cr³⁺ (S = 3/2) and Mn²⁺ (5 = 5/2) ions. The quantitative EPR findings suggest that all theS = 1/2 paramagnetic compounds investigated and MnSO₄ · H₂O (S = 5/2) are reliable primary standards. By contrast, none of the pure Cr³⁺ compounds proved useful as primary standards because of their large fine-structure terms or high Néel temperature that invalidated the simple Curie law. Application of quantitative EPR in the study of dilute MgO-MnO and α-Al₂O₃-Cr₂O₃ solid solutions, focussing on the circumstances making paramagnetic species undetectable, is reported. In MgO-MnO solid solutions of high surface area, detection problems arising from the variation of local site symmetry can be circumvented and almost all Mn²⁺ are detected only by reducing the surface area. In concentrated α-Al₂O₃-Cr₂O₃ solid solutions, magnetic interactions lead to paramagnetic species being undetectable.     

Characterization of colorants and opacifiers in roman glass mosaic tesserae through spectroscopic and spectrometric techniques

Several glass mosaic tesserae were recovered during the archeological excavation of the thermal baths at the ‘Villa dei Quintili’ in Rome and dated to the second century ad . This work reports the results of an archeometrical investigation performed, through a multi‐technique approach, on 19 colored opaque tesserae. The aims of the study were (1) the characterization of coloring and opacifying agents used for the production of the glass tesserae and (2) the definition of the technological processes involved. Colorimetric measurements allowed us to classify the tesserae in color groups, while the glassy matrix and the dispersed crystallites were characterized in detail through micro‐Raman spectroscopy, field emission scanning electron microscopy with energy dispersive X‐ray spectroscopy, laser ablation‐inductively coupled plasma‐mass spectrometry, and X‐ray powder diffraction analyses. Most of the glass shows the typical soda‐lime‐silicate composition (except for the orange and red tesserae). Raman results and elemental analysis prove the use of Sn–Pb antimonates to create yellow glass and of Ca‐antimonates for the white tesserae. A mixture of Sn–Pb antimonates and copper ions was used to obtain the emerald green color, while Ca‐antimonates were employed in both copper‐colored and cobalt‐colored blue glass to obtain different shades (blue‐green, dark, and light blue). X‐ray powder diffraction analyses reveal the presence of metallic copper (Cu⁰) and Cu₂O particles (cuprite) in red and orange tesserae, respectively. These results confirm the high technological level reached by the glassmakers of the Imperial Age. Copyright © 2014 John Wiley & Sons, Ltd.     

Copper Defects and Conductivity in Bi—Pb—Sr—Ca—Cu—O Glasses

Glass ceramics of the composition (Bi_0.8Pb_0.2)₄Sr₃Ca₃Cu₄O₈ prepared by the melt quenching technique and the crystalline phases produced by the rapid thermal annealing have been studied by electrical resistivity and electron paramagnetic resonance (EPR) measurements in the temperature range from liquid helium up to room temperature. The concentration of the EPR active Cu^2? paramagnetic centers decreases as conductivity increases for the glass ceramics and disappears after crystallization and the growth of superconducting phases, similar to bulk high-T_c superconductors. The KPR spectra of both glass and crystallized ceramics after short-time annealing indicate the coexistence of Cu^2? paramagnetic ions and the exchange coupled clusters.     

Relaxation of spin polarized 3He by magnetized ferromagnetic contaminants

In the first in a series of three papers on wall relaxation of spin polarized ³He we have reported on a breakdown of relaxation times which is observed after exposing the ³He containing glass cells to a strong magnetizing field. In this third paper we give a quantitative analysis of this phenomenon, based on magnetic signal detection by means of SQUIDs, on the pressure dependence of relaxation times in magnetized cells, as well as on Monte Carlo simulations of ³He-relaxation in a macroscopic dipole field. Our analysis allows to identify the contaminants as being aggregates of dust-like Fe₃O₄ particles (magnetite) with a radius R ? 10 mR \approx 10~\mu m and a remanent magnetic moment of the order of m ≈O(10 ^-10 ^{-10}~ A m²). The particles are located at or close to the inner glass surface.     

EPR and optical absorption studies of X-irradiated cobalt doped sodium chloride crystals

Sodium chloride crystals containing small concentrations of cobalt (< 10 ppm) do not show any EPR line. A thick block of crystal containing ～25 ppm of Co showed two partially resolved lines, with approximate g-values 2.036 and 2.011. These g-values are not close to those of Co⁺⁺ (4.0 to 4.5) in other crystals. On X-irradiation, pure NaCl crystals show a complex EPR spectrum. X-irradiated Co doped NaCl crystals showed an EPR line superimposed on the complex EPR spectrum. Cobalt doped highly pure crystals, on X-irradiation, showed an EPR line superimposed on the F center EPR line. The g-value of the former is 2.049±0.002 and half width is 62±3 gauss. These results combined with those of dielectric loss and optical studies show that X-irradiation of Co doped crystals produces new centers, labelled as S centers, which produce a dielectric loss peak, a decrease in electrical conductivity, an optical band at 210 nm and the EPR line. Possible models of the S centers are discussed.     

Dependence of the Silica Glass Parameters on the Fluence of Fast Neutrons

The results of comprehensive investigations into the influence of fast-neutron fluences on the silica glass parameters are presented. In particular, the dose dependences of the parameters are measured by optical (luminescence, absorption, EPR, IR, and refraction), dielectric, and x-ray spectroscopy methods over a wide range of fluences from 10¹⁷ to 10²¹ cm^–2. It is concluded that the specific features in the formation of radiation-induced defects and silica damages are most likely due to the neutron-induced phase transition.     

Fullerene C<Subscript>70</Subscript> Triplet Zero-Field Splitting Parameters Revisited by Light-Induced EPR at Thermal Equilibrium

Continuous-wave (CW) electron paramagnetic resonance (EPR) and echo-detected (ED) EPR spectra of triplet state of fullerene C₇₀ in molecular glasses of decalin, o-terphenyl and toluene, and in polymethylmethacrylate polymer were obtained under continuous light illumination. Temperature was high enough so that the EPR spectra corresponded to thermal equilibrium between the spin sublevels. The comparison of CW EPR and ED EPR data has shown that pseudorotation in the ³C₇₀ frame does not remarkably affect deriving the zero-field splitting (ZFS) D and E parameters from the EPR spectra. ³C₇₀ EPR spectra were simulated at 77 K fairly well using the distribution of the ZFS D and E parameters. These distributions may be caused by the inhomogeneity of the glassy matrix surrounding, which affects the Jahn–Teller distortions of ³C₇₀ molecules (D-strain and E-strain).     

EPR Study of 5-Chlorosalicylate-Cu(II)-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Diethylnicotinamide Ternary Complex Systems in Frozen Water–Methanol Solutions

As a continuation of our previous study of Cu(II) ternary complexes, two new systems containing 5-chlorosalicylic acid (5-ClsalH) and different Cu(II) salts, with varying N,N-diethylnicotinamide (denia) concentrations, system III [CuSO₄(aq) + 2(5-ClsalH(solv)) + xdenia(l)] and system IV [Cu(ac)₂(aq) + 2(5-ClsalH(solv)) + xdenia(l)], where x = 0, 2, 4, 6 and 8, were prepared. The effects of Cu(II) salts containing anions of different basicity and N-donor ligand (denia) with varying ligand-to-metal ratio (x) on the formation of resulting complexes were studied by electron paramagnetic resonance (EPR) spectroscopy in frozen water–methanol solutions. Well-resolved ¹⁴N superhyperfine splitting lines (nonet) in the perpendicular region of the second-derivative axially symmetric Cu(II) EPR spectra indicated that for x > 4 in system III and for x ≥ 2 in system IV, four equivalent nitrogens could be coordinated to the central Cu(II) ions in the equatorial plane. Such information cannot be obtained by EPR spectroscopy of powder samples of the given Cu(II) complex systems. The differences between denia and ronicol containing Cu(II) complexes are discussed.     

EPR studies of highly pure,pure and doped chromium oxide powders

Abstract

EPR absorption measurements on ‘pure’, highly pure and A1₂O₃ doped Cr₂O₃ powder have been made. The EPR absorption in the ‘pure’ powders obtained below Ntel temperature is shown to be due to background magnetic impurities present in the powders and not due to superparamagnetism as suggested by earlier authors. No EPR absorption could be observed below Nkl temperature in highly pure powders (total background impurity concentration less than 5 ppm). ‘Pure’ powders or highly pure powders mixed with A1₂O₃ powder and annealed at high temperatures showed a symmetrical EPR absorption line at room temperature. The shape and the g value of this line are practically the same as those obtained for Cr³⁺ ions in Cr₂O₃ above Nee1 temperature or in other nonmagnetic crystals. It is concluded from these results that the impurities diffuse into Cr₂O₃ powder, the antiferro-magnetic coupling between some of the Cr³⁺ ions is broken and these Cr³⁺ ions become paramagnetic, even when the bulk of the material is in antiferromagnetic state. The variation of half-width of EPR lines with impurity concentration shows that the dipolar coupling between Cr³⁺ ions decreases with the increase in impurity concentration and when the impurity concentration is high the Néel temperature seems to shift to lower temperatures. A longer heat treatment of the ‘pure’ B powder resulted in the production of shining metal particles in the powder. The EPR of this powder showed excessive increase in the intensity of EPR absorption when the temperature of the powder was raised to a value just above the Néel temperature. A comparison of these reuslts with the work of earlier authors suggests that the shinning metal particles are those of chromium metal and are responsible for this increase in EPR absorption.     

EPR Investigation of Radical-Production Cross Sections for Sucrose and L-alanine Irradiated with X-rays and Heavy-ions

Using electron paramagnetic resonance (EPR), we investigated stable radical-production cross sections (σ) of sucrose and L-alanine radicals produced by heavy-ion irradiations with various linear energy transfers (LET). The heavy-ion irradiation results were compared with those of X-ray irradiation at the same dose. The EPR signal areas for the two compounds showed a linear relation with the absorbed dose, as well as a logarithmic correlation with the LET. Further analysis was carried out for the radical-production cross section, which showed that stable radicals of the two compounds were produced through collisions of several particles with a single molecule. The relative σ value of sucrose for C ion irradiation was (1.29 ± 0.64) × 10⁻¹² μm². The σ value of alanine for C ion irradiation was (6.83 ± 0.42) × 10⁻¹³ μm². Considering the structural molecular sizes of sucrose and alanine, the σ values are similar. In addition, a comparison of the EPR results for the C ions and X-rays at 50 Gy dose was made. Sucrose spin concentrations produced by C ions at the LET value of 13.1 keV/μm and X-rays were similar unlike alanine. Thus, the noble EPR results with X-ray and heavy-ion irradiations imply that sucrose can be useful as a radiation indicator.