Studies of the EPR and optical spectra for Cr3+-doped KAl(MoO4)2 crystal

The EPR parameters (zero-field splitting D and g factors g₆, Δg = g₆ − g_⊥) and the first excited-state splitting δ(²E) for Cr³⁺-doped KAl(MoO₄)₂ crystal are calculated from the high-order perturbation formulas. In the calculations, the parameters are obtained from the optical spectra and structural data of the studied system. The results show good agreement with the observed values.     

EPR,optical absorption and luminescence studies of Cr3+-doped antimony phosphate glasses

Antimony phosphate glasses (SbPO) doped with 3 and 6 mol% of Cr³⁺ were studied by Electron Paramagnetic Resonance (EPR), UV–VIS optical absorption and luminescence spectroscopy. The EPR spectra of Cr³⁺-doped glasses showed two principal resonance signals with effective g values at g = 5.11 and g = 1.97. UV–VIS optical absorption spectra of SbPO:Cr³⁺ presented four characteristics bands at 457, 641, 675, and 705 nm related to the transitions from ⁴A₂(F) to ⁴T₁(F), ⁴T₂(F), ²T₁(G), and ²E(G), respectively, of Cr³⁺ ions in octahedral symmetry. Optical absorption spectra of SbPO:Cr³⁺ allowed evaluating the crystalline field Dq, Racah parameters (B and C) and Dq/B. The calculated value of Dq/B = 2.48 indicates that Cr³⁺ ions in SbPO glasses are in strong ligand field sites. The optical band gap for SbPO and SbPO:Cr³⁺ were evaluated from the UV optical absorption edges. Luminescence measurements of pure and Cr³⁺-doped glasses excited with 350 nm revealed weak emission bands from 400 to 600 nm due to the ³P₁ → ¹S₀ electronic transition from Sb³⁺ ions. Cr³⁺-doped glasses excited with 415 nm presented Cr³⁺ characteristic luminescence spectra composed by two broad bands, one band centered at 645 nm (²E → ⁴A₂) and another intense band from 700 to 850 nm (⁴T₂ → ⁴A₂).     

Synthesis,EPR and optical spectroscopy of the Cr-doped tetraborate glasses

Electron paramagnetic resonance (EPR), optical absorption and photoluminescence spectra as well as luminescence kinetics of the Li₂B₄O₇:Cr and KLiB₄O₇:Cr tetraborate glasses were investigated at T = 300 K. The Li₂B₄O₇:Cr and KLiB₄O₇:Cr glasses containing 0.4 and 1.6 mol.% Cr₂O₃ of high optical quality were obtained from polycrystalline compounds by fast cooling of the melts. The X-band EPR spectroscopy shows that the Cr impurity is incorporated in the tetraborate glass network as isolated Cr³⁺ centers and Cr³⁺–Cr³⁺ pairs coupled by magnetic dipolar and exchange interactions. The EPR spectral parameters (g_eff and ΔB_pp) of both Cr³⁺ and Cr³⁺–Cr³⁺ centers in the Li₂B₄O₇:Cr and KLiB₄O₇:Cr glasses were measured and analyzed. All transitions in optical absorption, luminescence excitation and emission spectra of these glasses are identified. Broad complex bands that peak near 615, 405, and 350 nm in optical absorption and luminescence excitation spectra correspond to the ⁴A_2g(F) → ⁴T_2g(F), ⁴A_2g(F) → ⁴T_1g(F), and ⁴A_2g(F) → ⁴T_1g(P) spin-allowed transitions of the Cr³⁺ centers in distorted octahedral sites of the tetraborate glass network. The octahedral (cubic) crystal field strength (10Dq) and Racach parameters (B and C) for Cr³⁺ centers in Li₂B₄O₇:Cr and KLiB₄O₇:Cr glasses are estimated. Narrow and broad emission bands in red – NIR regions are assigned to the ²E_g(F) → ⁴A_2g(F) (R₁ line) and ⁴T_2g(F) → ⁴A_2g(F) (electron-vibration) transitions, which correspond to the Cr³⁺ centers in high-field and low-field sites, respectively. All observed emission bands are characterized by non-exponential decay. Measured average lifetimes and local structure of the Cr³⁺ centers in high-field and low-field sites of the Li₂B₄O₇:Cr and KLiB₄O₇:Cr glass network have been discussed.     

Electron paramagnetic resonance (EPR) investigations of the local environment around Co2+ ions doped in PbMoO4 single crystals – Correlation with optical studies

The electron paramagnetic resonance (EPR) measurements of PbMoO₄ single crystals doped with Co²⁺ ions (0.5 wt.%) carried out at temperature range 10–12 K are reported. The observed spectra reveal evidently two major groups of EPR spectra, each group consists of eight hyperfine structure components associated with the Co nuclear spin I = 7/2. Additionally, EPR spectra of the unintentional impurities have been observed, which have been assigned to Nd³⁺ ions in PbMoO₄. The analysis of the various characteristic features of the EPR spectra as well as our earlier optical absorption studies of Co²⁺:PbMoO₄ indicate that the Co²⁺ ions are located at two crystallographically distinct complexes, denoted Co²⁺(α) and Co²⁺(β). The fictitious ‘spin’ S′ = ½ has been assigned to the observed ground Kramers doublet state of each of the two Co²⁺ complexes tentatively identified as located at the Mo sites in PbMoO₄. The spin Hamiltonian parameters for Co²⁺ (S′ = ½) ions in PbMoO₄, including the components of the Zeeman and hyperfine structure tensors g_ij and A_ij, respectively, are experimentally determined for the first time. Comparison of our results with the values of g_ij and A_ij for Co²⁺ ions in other structurally similar compounds further strengthens this conclusion. Correlation of the present results with those obtained earlier from optical studies is discussed. Alternative assignments of the ground states and options for the origin of the ‘spin’ S′ = ½ for Co²⁺ ions in PbMoO₄ will be considered in a subsequent paper.     

An innovative process to fabricate copper/diamond composite films for thermal management applications

Diamond dispersed copper matrix (Cu/D) composite films with strong interfacial bonding were produced by tape casting and hot pressing without carbide forming additives. The tape casting process offers an original solution to obtain laminated materials with accurate thickness control, smooth surface finish, material net-shaping, scalability, and low cost. This study presents an innovative process of copper submicronic particles deposition onto diamond reinforcements prior to densification by hot pressing. Copper particles act as chemical bonding agents between the copper matrix and the diamond reinforcements during hot pressing, thus offering an alternative solution to traditionnal carbide-forming materials in order to get efficient interfacial bonding and heat-transfer in Cu/D composites. It allows high thermal performances with low content of diamond, thus enhancing the cost-effectiveness of the materials. Microstructural study of composites by scanning electron microscopy (SEM) was correlated with thermal conductivity and thermal expansion coefficient measurements. The as-fabricated films exhibit a thermal conductivity of 455 W m^?1 K^?1 associated to a coefficient of thermal expansion of 12 × 10^?6 °C^?1 and a density of 6.6 g cm^?3 with a diamond volume fraction of 40%, which represents a strong enhancement relative to pure copper properties (λ_Cu = 400 W m^?1 K^?1, α_Cu = 17 × 10^?6 °C^?1, ρ_Cu = 8.95 g cm^?3). The as-fabricated composite films might be useful as heat-spreading layers for thermal management of power electronic modules.     

Flux growth and thermal properties of LiBaB9O15 single crystal

A large LiBaB₉O₁₅ single crystal has been grown by the top-seeded solution growth (TSSG) method using a Li₂Mo₃O₁₀ flux system. The crystal obtained exhibits (1 1 0), (1 1 3) and (1 0 2) faces. For the first time, thermal properties of the as-grown crystal, including thermal expansion, specific heat and thermal conductivity, have been investigated as a function of temperature. The specific heat of the LiBaB₉O₁₅ crystal was measured to be 0.663–1.110 J g^?1 K^?1 over the temperature range of 20–400 °C. The crystal exhibits thermal expansion along the a- and b-axis, coupled with thermal contraction along the c-axis, over the measured temperature range of 25–500 °C. The average thermal expansion coefficients along the a- and c-axis of the LiBaB₉O₁₅ crystal from 25 to 500 °C are calculated to be α_a = 6.56 × 10^?6 K^?1 and α_c = ?4.82 × 10^?6 K^?1, respectively.     

Improvement of dry float–sink separation of smaller sized spheres by reducing the fluidized bed height

In this study, the influence of the fluidized bed height on the float–sink of different sized spheres in a gas–solid fluidized bed was investigated. Fluidized beds with heights h = 200, 150, 100 and 50 mm were prepared using a cylindrical column of inner diameter = 290 mm and a mixture of zircon sand and iron powder as the fluidized medium. Float–sink experiments were carried out using density adjusted spheres of diameter D_sp = 40, 30, 20 and 10 mm. It was found that the float–sink performance at D_sp ?20 mm is not affected by the height of the bed, and the sharpness of separation (the density range where spheres neither float nor sink completely) is less than or equal to 200 kg/m³. In the case of D_sp = 10 mm, the sharpness of separation is a larger value (1100 kg/m³ at h = 200 mm), whereas it decreases with decreasing h and is 400 kg/m³ at h = 50 mm. The fluctuation of the surface height of the fluidized bed was visually recorded. The fluctuation is reduced by reducing h. The fluctuation vs. h correlates with the sharpness of separation at D_sp = 10 mm vs. h. These results indicate that the dry float–sink separation of smaller sized spheres is improved as the fluctuation of fluidized bed surface is decreased by reducing the fluidized bed height.     

The origin of defects formation in nanosized zirconia

In the present work, we provide evidence of an increase in the Zr³⁺ paramagnetic center concentration under colloidal transformation in ZrO₂ prepared by the totally inorganic sol–gel method. The samples of thermally treated (100–950 °C in air) ZrO₂ precipitates and dried sol–gel products—xerogels—were examined by TEM, XRD, DTA, EPR and IR-spectroscopy. Under the same heat treatment condition, the concentration of Zr³⁺ (axially symmetric signal at g_⊥ = 1.977–1.979 and g₆ = 1.958–1.963) became higher in the xerogel samples rather than in precipitate samples and reached the maximum (∼ 10¹⁸ g^− 1 in xerogel) after calcinations at 500 °C in air.     

Synthesis and characterization of a new p-phenylenediammonium dihydrogenmonophosphate [p-NH3C6H4NH3][H2PO4]2

Chemical preparation, crystal structure and NMR spectroscopy of a new organic cation p-phenylenediammonium monophosphate [p-NH₃C₆H₄NH₃][H₂PO₄]₂ are presented. This new compound crystallizes in the orthorhombic system, with the space group Pnma and the following parameters: a = 7.970 (2) Å; b = 22.770 (7) Å; c = 7.000 (7) Å, V = 1270.3 (11) Å³, Z = 4 and D_x = 1.590 g cm⁻³. The crystal structure has been determined and refined to R = 0.043 and R_(w) = 0.057 using 2623 independent reflections. The structural arrangement can be described as inorganic layers of (H₈P₄O₁₆)⁴⁻ units, parallel to (a, c) planes. The organic groups (p-H₃NC₆H₄NH₃)²⁺are anchored between the phosphoric layers to form a three-dimensional infinite network. This compound is also investigated by IR and solid-state ¹H, ¹³C and ³¹P MAS NMR spectroscopies. The ab initio method is used in the calculation of chemical shifts.     

Electrochemical properties of 0.3Li2MnO3·0.7LiNi0.5Mn0.5O2 composite cathode powders prepared by large-scale spray pyrolysis

0.3Li₂MnO₃·0.7LiNi_0.5Mn_0.5O₂ composite cathode powders with a mixed-layer crystal structure comprising Li₂MnO₃ and LiNi_0.5Mn_0.5O₂ phases are prepared by spray pyrolysis. The composition of the cathode powders is found to be Li_1.19Ni_0.39Mn_0.61O₂ by ICP analysis. At a constant current density of 30 mA g^?1, the initial discharge capacities of the composite cathode powders post-treated at 700, 750, 800, and 850 °C are 177, 202, 215, and 212 mAh g^?1, respectively. The discharge capacity of the composite cathode powders post-treated at 800 °C decreases from 215 mAh g^?1 to 205 mAh g^?1 by the 40th cycle, in which the capacity retention is 95%. The first cycle has a low Coulombic efficiency of 75%. However, in the subsequent cycles, the Coulombic efficiency is retained at nearly 100%. The dQ/dV curves show that Mn exists as Mn⁴⁺ in the sample. The Mn⁴⁺ ions in the cathode powders become increasingly active as the cycle number increases and participate in the electrochemical reaction.     

Thermal conductivity and Kapitza resistance of cyanate ester epoxy mix and tri-functional epoxy electrical insulations at superfluid helium temperature

In the framework of the European Union FP7 project EuCARD, two composite insulation systems made of cyanate ester epoxy mix and tri-functional epoxy (TGPAP-DETDA) with S-glass fiber have been thermally tested as possible candidates to be the electrical insulation of 13 T Nb₃Sn high field magnets under development for this program. Since it is expected to be operated in pressurized superfluid helium at 1.9 K and 1 atm, the thermal conductivity and the Kapitza resistance are the most important input parameters for the thermal design of this type of magnet and have been determined in this study. For determining these thermal properties, three sheets of each material with different thicknesses varying from 245 to 598 μm have been tested in steady-state condition in the temperature range of 1.6–2.0 K. The thermal conductivity for the tri-functional epoxy (TGPAP-DETDA) epoxy resin insulation is found to be k = [(34.2 ± 5.5)?T ? (16.4 ± 8.2)] × 10^?3 Wm^?1 K^?1 and for the cyanate ester epoxy k = [(26.8 ± 4.8)?T ? (9.6 ± 5.2)] × 10^?3 Wm^?1 K^?1. For the Kapitza resistance, R_k, the best curve fitting the experimental data is described by R_k = (3057 ± 593) × 10^?6?T (?1.79 ± 0.34) m² KW^?1 for the TGPAP-DETDA insulation and R_k = (4114 ± 971) × 10^?6?T (?1.73 ± 0.41) m² KW^?1 for the cyanate ester epoxy insulation. Our results are compared with other epoxy based composite electrical insulation found in the literature.     

Mixed alkali effect in Li2O–Na2O–B2O3 glasses containing Fe2O3—An EPR and optical absorption study

This paper reports the interesting results on mixed alkali effect (MAE) in xLi₂O–(30-x)Na₂O–69.5B₂O₃ (5 ≤ x ≤ 28) glasses containing Fe₂O₃ studied by electron paramagnetic resonance (EPR) and optical absorption techniques. The EPR spectra in these glasses exhibit three resonance signals at g = 7.60, 4.20 and 2.02. The resonance signal at g = 7.60 has been attributed to Fe³⁺ ions in axial symmetry sites whereas the resonance signal at g = 4.20 is due to isolated Fe³⁺ ions in rhombic symmetry site. The resonance signal at g = 2.02 is due to Fe³⁺ ions coupled by exchange interaction. It is interesting to observe that the number of spins participating in resonance (N) and its paramagnetic susceptibility (χ) exhibits the mixed alkali effect with composition. The present study also gives an indication that the size of alkali ions we choose in mixed alkali glasses is also an important contributing factor in showing the mixed alkali effect. It is observed that the variation of N with temperature obeys Boltzmann law. A linear relationship is observed between 1/χ and T in accordance with Curie–Weiss law. The paramagnetic Curie temperature (θ_p) is negative for the investigated sample, which suggests that the iron ions are antiferromagnetically coupled by negative super exchange interactions at very low temperatures. The optical absorption spectra exhibit only one weak band corresponding to the transition ⁶A_1g(S) → ⁴A_1g(G); ⁴E_g(G) at 446 nm which is a characteristic of Fe³⁺ ions in octahedral symmetry.     

An electron spin resonance study of Mn2+ doped calcium hydrazine carboxylate monohydrate

Single crystals of calcium hydrazine carboxylate, monohydrate have been studied by ESR of Mn²⁺ doped in the calcium sites. X-band ESR indicated a large crystal field splitting necessitating experiments at Q band. The analysis shows two magnetically inequivalent (but chemically equivalent) sites withg _xx = 2.0042±0.0038,g _yy=2.0076 ±0.0029,g _zz=2.0314±0.001,A _zz=0.0099±0.0002 cm⁻¹,A _xx=0.0092±0.0002 cm⁻¹,A _yy=0.0082±0.0002 cm⁻¹,D=3/2D _zz=0.0558±0.0006 cm⁻¹, andE=1/2 (D _yy−D _yy)=0.0127±0.0002 cm⁻¹. One of the principal components of the crystal field, (D _zz), is found to be along the Ca ↔ Ca direction in the structure and a second one, (D _xx), along the perpendicular to the plane of the triangle formed by three neighbouring calciums. TheA tensor is found to have an orientation different from that of theg andD tensors reflecting the low symmetry of the Ca²⁺ sites.     

EPR and vibrational studies of YVO4:Tm3+, Yb3+ single crystal

A well oriented YVO₄ single crystal, with 5% Yb³⁺ and 2% Tm³⁺ nominal doping, was investigated using the Raman and EPR techniques.The EPR measurements suggest that Yb³⁺ ions occupy eight-coordinated Y³⁺ sites forming bisdisphenoids of the D_2d symmetry. An inhomogeneous distribution of rare-earth ions leads to a significant distortion of the local point symmetry (C₁). It seems that strong dipole–dipole interactions between Yb³⁺ ions are responsible for the distortion. As a result, two types of ytterbium magnetic centers appear. They correspond to paired magnetic centers and distorted isolated paramagnetic centers that are strongly sensitive to the magnetic field directions and some imperfections of the crystal. Pair centers can be recorded through the rotation around the c-crystal axis, whereas isolated centers can be measured when the crystal is rotated around the a-crystal axis. With the increasing temperature, the ytterbium signal disappeared at about 23 K and a group of narrow lines became visible. These lines, observed in the range of 240–550 mT, correspond to the Gd³⁺ (S = 7/2) ions, doped to the structure unintentionally from the basic materials.     

Crystal structure,thermal analysis and IR spectrometric investigation of l-tyrosine hydrazide diphosphate monohydrate

The monoclinic crystal structure of (C₉H₁₅N₃O₂)₂P₂O₇·H₂O denoted DLTHDP [a = 14.626(1), b = 6.1990(2), c = 14.562(1) Å, β = 97.289(3)°, Z = 2, monoclinic P2₁, D_cal = 1.508, D_mes = 1.49 g cm⁻³] has been solved using direct methods and refined to a reliability factor R = 4.37% for 2079 independent reflections. The DLTHDP structure can be described by infinite polyanions [P₂O₇·H₂O]_n⁴ⁿ⁻ organized in chains parallel to the b-direction and located at z = 1/2, alternating with organic cations associated in ribbons spreading along the a-direction. Multiple hydrogen bonds originating from amine, hydroxyl groups and water molecules donors [NH…O(N) and O(W)H…O] connect the different components of the lattice. The IR data of DLTHDP is reported and discussed according to the theoretical group analysis and by comparison with IR results of similar compounds. The coupled thermogravimetric analysis (TGA)–differential thermal analysis (DTA) thermal study shows the departure of one water molecule, confirming the hydrated character of this compound.     

Effect of symmetry reduction on the electronic transitions in polytypic GdAl3(BO3)4:Eu:Tb crystals

The existence of a recently described monoclinic phase (C2/c, Z = 8) (Beregi et al., 2012) in addition to the well-known Huntite type rhombohedral (R32) polytypic modification of the GdAl₃(BO₃)₄ (GAB) crystal at room temperature provides a unique possibility to investigate the incorporation of rare earth dopants into slightly modified crystal lattice by spectroscopic methods. In these characteristic GAB structures the dopant ions, e.g. Tb³⁺ or Eu³⁺, possess slightly different neighbor geometries and local symmetries. The Tb³⁺: ⁷F₆ → ⁵D₄ and Eu³⁺: ⁷F_0,1,2 → ⁵D_0,1,2 electronic transitions were successfully identified in the absorption spectra using polarization, concentration and temperature dependent measurements in both polytypic modifications. The positions of the investigated Tb lines are shifted by up to 10 cm⁻¹ due to symmetry changes. In addition, some of the Eu lines show splittings of about 4–30 cm⁻¹ as a consequence of the change of the local environment. From the room temperature absorption measurements some of the low energy crystal field levels of ⁷F and ⁵D states of the Eu³⁺ ions were successfully determined for both modifications.     

Physical and spectroscopic properties of multi-component Na2O–PbO–Bi2O3–SiO2 glass ceramics with Cr2O3 as nucleating agent

Transparent glass ceramics, synthesized from melt quenching followed by heat treatment, of the composition 10Na₂O–30PbO–10Bi₂O₃–(50 − x)SiO₂:xCr₂O₃ (mol%), where 0 ⩽ x ⩽ 0.5, were characterized with XRD, DTA, SEM and EDS. Physical and spectroscopic studies, viz., optical absorption, electron paramagnetic resonance (EPR), FTIR and Raman were investigated. The characterization of the host glass ceramic has revealed that the formation of a major phase of sodium silicate along with two minor phases such as lead silicate and bismuth oxide. By integrating Cr₂O₃ to the host glass additional crystal phases viz., NaCrO₂, Na₂Cr₂O₇ and Pb(CrO₄) which are the complexes of Cr³⁺ and Cr⁶⁺ ions were also developed. As the concentration of nucleating agent is increased, a part of the Cr⁶⁺ ions is found to reduce in to Cr³⁺ ions. Spectroscopic studies have revealed that with an increase in the concentration of Cr₂O₃ from 0.1 to 0.5 mol%, there is a gradual increase in the intensity of vibrational modes of various asymmetric structural units of silicate, bismuthate and chromate in the glass ceramic network at the expense of symmetrical structural units. The analysis of the results of these studies has indicated that in the samples containing higher concentration of Cr₂O₃, chromium ions exists predominantly in Cr³⁺ state and occupy the octahedral positions in glass ceramic matrix and such glass ceramic samples are suitable for lasing action.     

Vapor growth of CdSe:Cr and CdS:Cr single crystals for mid-infrared lasers

Single crystals of CdSe:Cr and CdS:Cr with the doping level up to 10¹⁹ cm⁻³ were grown by a vapor phase contact-free technique. An efficient room-temperature pulsed and continuous wave (CW) lasing with the CdSe:Cr crystal was achieved. First a pulsed lasing with the CdS:Cr crystal was also demonstrated. The slope efficiency on the absorbed energy was as high as 46.5% for Cr²⁺:CdSe and 39% for Cr²⁺:CdS lasers. Using an intra-cavity prism, the Cr²⁺:CdSe laser wavelength was continuously tuned from 2.26 to 3.61 μm while the Cr²⁺:CdS laser from 2.2 to 3.3 μm. For the laser wavelength, the crystal passive loss coefficient was estimated to be smaller than 0.045 cm⁻¹ for CdSe:Cr crystals and 0.039 cm⁻¹ for CdS:Cr crystals. For the Cr²⁺:CdSe laser, the CW output power up to 1.07 W was achieved.     

Kinetics of elimination and distribution in blood and liver of biocompatible ferrofluids based on Fe3O4 nanoparticles: An EPR and XRF study

In this study, we evaluated the biodistribution and the elimination kinetics of a biocompatible magnetic fluid, Endorem™, based on dextran-coated Fe₃O₄ nanoparticles endovenously injected into Winstar rats. The iron content in blood and liver samples was recorded using electron paramagnetic resonance (EPR) and X-ray fluorescence (XRF) techniques. The EPR line intensity at g = 2.1 was found to be proportional to the concentration of magnetic nanoparticles and the best temperature for spectra acquisition was 298 K. Both EPR and XRF analysis indicated that the maximum concentration of iron in the liver occurred 95 min after the ferrofluid administration. The half-life of the magnetic nanoparticles (MNP) in the blood was (11.6 ± 0.6) min measured by EPR and (12.6 ± 0.6) min determined by XRF. These results indicate that both EPR and XRF are very useful and appropriate techniques for the study of kinetics of ferrofluid elimination and biodistribution after its administration into the organism.     

Temperature dependence of spectral positions and widths of 5DJ → 7FJ fluorescence lines originating from Sm2+ ions in SrFCl crystals

The temperature dependence of the spectral positions and widths of the photoluminescence lines corresponding to the ⁵D₀ → ⁷F₀, ⁵D₀ → ⁷F₁ and ⁵D₁ → ⁷F₀ electronic transitions in Sm²⁺-doped SrFCl crystal was measured between 87 and 625 K at ambient pressure. The temperature dependence of the homogeneous line width Γ_h(T) for all these transitions in the whole temperature range used can be described by the two-phonon Raman scattering of acoustic phonons with the Debye temperature T_D ≈ 230 K. Comparison of the temperature- and pressure-induced shifts revealed why all the emission lines studied show the blue temperature shifts. It is so because a greater part of the line shift is caused by the thermal expansion of the host crystal and not by enhancement of the electron–phonon coupling with increasing temperature.