Cu2+ ions in sodium fluoride-sodium borate glasses studied by EPR and optical absorption techniques

Electron paramagnetic resonance (EPR) and optical absorption spectra of Cu²⁺ ions in 80Na₂B₄O₇-(20 – x)NaF – xCuO (NFNB) glass system with 0 x 6 mol% have been studied. EPR spectra of all the glass samples exhibit resonance signals characteristic of Cu²⁺ ions. The values of spin-Hamiltonian parameters indicate that the Cu²⁺ ions in sodium fluoride-sodium borate (NFNB) glasses were present in octahedral sites with tetragonal distortion. The number of spins (N) participating in resonance was calculated as a function of temperature for NFNB glass sample containing 1 mol% of Cu²⁺ ions and the activation energy was calculated. From the EPR data, the paramagnetic susceptibility () was calculated at various temperatures and the Curie constant was calculated from the 1/ – T graph. The optical absorption spectra of these samples show a broad absorption band centered at 13280 cm^–1 which is assigned to the ² B _1g ² B _2g transition of Cu²⁺ ions in distorted octahedral sites. The optical band gap energy (E _opt) and Urbach energy (E) are calculated from their ultraviolet edges. It is observed that as the copper ion concentration increases, E _opt decreases while E increases. This has been explained as due to the creation of additional localized states by CuO, which overlap and extend in the mobility gap of the matrix. By correlating the EPR and optical data, the molecular orbital coefficients have been evaluated.     

EPR study of Cu2+ in Na2O-NaF-B2O3-Bi2O3 glasses

Electron paramagnetic resonance (EPR) studies have been performed on the glass system (30–x) NaF-xNa₂O-50B₂O₃-20Bi₂O₃ doped with CuO as a paramagnetic probe. The calculated g values indicate that Cu²⁺ is in a tetragonally elongated octahedral co-ordination, and the Jahn-Teller character gives rise to anisotropic hyperfine structure. The spin-Hamiltonian parameters and -bonding parameter, ², are calculated. Varying the fluoride ion concentration and its effect on these parameters is also discussed.     

Electron spin resonance and optical absorption spectra of Cu2+ ions in Na2SO4-ZnSO4 glasses

Electron spin resonance (ESR) and optical absorption spectra of Cu²⁺ ions in Na₂SO₄-ZnSO₄ glasses have been studied. The ESR spectra of Cu²⁺ ion-doped glasses exhibited a pronounced peak atg=2.07 and a shallow quadruplet atg=2.35, the latter arising from the hyperfine splitting of g. ESR spectra of Cu²⁺ ion-doped glasses were also studied by varying the concentration of Cu²⁺ions, temperature and composition of the glasses. The optical absorption spectra exhibited a broad absorption band in the near infrared region, which is attributed to²B_1g²B_2g transition. By correlating the ESR and optical absorption data, the bonding orbital coefficients ² and ₁ ² for Cu²⁺ ions have been evaluated.     

EPR and optical absorption of Cr3+ in binary Na2O-B2O3 glasses

The optical absorption and EPR spectra of Cr³⁺ in binary sodium borate glasses have been studied as functions of chromium concentration and Na₂O/B₂O₃ ratio in the glass; the ligand field and EPR parameters have been calculated and were found to be independent of Cr₃₊ concentration in any particular glass. In low-alkali borate glasses (Na₂O = 11 or 14 mol %) a single symmetrical EPR line was observed with g _¦=g =1.984±0.001 corresponding to perfect octahedral symmetry of the Cr³⁺ ion in these glasses. With increasing Na₂O content of the glass, the EPR line becomes more asymmetric (characteristic two-peaked pattern); this has been explained as being due to axial elongation of the six co-ordinated Cr³⁺-complex in these glasses.     

Interaction between a dislocation and an impurity in KCl: Mg2+ single crystals

The interaction between a dislocation and the impurity in KCl: Mg²⁺ (0.035 mol% in the melt) was investigated at 77–178 K with respect to the two models: one is the Fleischer's model and the other the Fleischer's model taking account of the Friedel relation. The latter is termed the F-F. The dependence of strain-rate sensitivity due to the impurities on temperature for the specimen was appropriate to the Fleischer's model than the F-F. Furthermore, the activation enthalpy, H, for the Fleischer's model appeared to be nearly proportional to the temperature in comparison with the F-F. The Friedel relation between effective stress and average length of the dislocation segments is exact for most weak obstacles to dislocation motion. However, above-mentioned results mean that the Friedel relation is not suitable for the interaction between a dislocation and the impurity in the specimen. Then, the value of H(T _c) at the Fleischer's model was found to be 0.61 eV. H(T _c) corresponds to the activation enthalpy for overcoming of the strain field around the impurity by a dislocation at 0 K. In addition, the Gibbs free energy, G ₀, concerning the dislocation motion was determined to be between 0.42 and 0.48 eV on the basis of the following equation ln / = G ₀/(kT_p0)1 – (T/T _c)^{1/2 –1}(T/T _c)^1/2 + ln ₀/where k is the Boltzmann's constant, T the temperature, T _c the critical temperature at which the effective stress due to the impurities is zero, _p0 the effective shear stress without thermal activation, and ₀ the frequency factor.     

Thermal stability and optical transition of Er3+ in sodium-lead-germanate glasses

The thermal stability and spectroscopic properties of Er³⁺-doped Na₂O-GeO₂-PbO glasses were investigated experimentally. The thermal analysis results show that the thermal stability of the investigated glasses is improved with replacing GeO₂ by PbO. Subsequently, Judd-Ofelt (J-O) approach was applied to the room temperature absorption of Er³⁺ (4f ¹¹) transitions to determine J-O intensity parameters. The reduced values of ₂ with the substitution of PbO for GeO₂ indicate the decrease of covalency of Er—O bonding. The stimulated emission cross section of the ⁴ I _13/2 ⁴ I _15/2 transition increases as a consequence of the increase of refractive index of glass hosts and the narrowing of fluorescence bandwidth with the increase of PbO. The abnormal large emission cross section and large bandwidth in the Na₂O-0.8GeO₂-0.1PbO glass arises from the change of germanium coordination with oxygen.     

EPR study of polycrystalline superconductors with YBa2Cu3O7 structure

Electron paramagnetic resonance (EPR) of Gd³⁺, Eu²⁺, and copper ions has been investigated in the high-T_c superconductor with YBa₂Cu₃O_7– structure. It has been established that the system is heterogeneous at 0.150.5 and consists of metallic and dielectric regions. The former arises due to oxygen enrichment while the later due to oxygen deficiency. The integral of exchange interaction between Gd³⁺ localized moments and conduction electrons J_sf=0.016 eV has been determined from the normal state temperature dependence of Gd³⁺ EPR linewidth for metallic regions. T_c depression by gadolinium-localized moments for GdBa₂Cu₃O_7– was estimated to be T_c–2K. Anomalies in linewidth temperature dependence upon transition from the normal to the superconducting state have given information about the value and temperature behavior of the superconductor's energy gap. The model, which gives the opportunity to understand some peculiarities of the EPR signal for YBa₂Cu₃O_7– samples, is proposed in terms of several bottlenecked spinsubsystems: spin-liquid in CuO planes and Cu²⁺-O^– and Cu²⁺-O^2– fragments in CuO chains.     

Energy Scales in the High-Tc Superconductor YBa2Cu3O6+x

The optical conductivity sum rule is used to examine the evolution of the spectral weight N() in both the normal and superconducting states of optimally and underdoped YBa₂Cu₃O_6+x along the a axis. Differences in N() above and below T _c allow the strength of the superconducting condensate _s to be determined. In the optimally-doped material, _s is fully formed at energies comparable to the full superconducting gap maximum (0.1 eV), while in the underdoped material the energy scale for convergence is considerably higher (0.6 eV). This difference is discussed in terms of normal-state properties.     

Optical and esr spectra of titanium (III) in Na2O-B2O3 and Na2O-P2O5 glasses

The optical absorption and the esr spectra of titanium(III) in binary Na₂O-B₂O₃ and Na₂O-P₂O₅ glasses have been studied. Titanium(III) produces two optical absorption bands around 20 000 and 14 000 cm^–1 which are assigned to the²B_2g ²B_1g and²B_2g ²A_1g transitions respectively of Ti³⁺ in a tetragonally distorted octahedral environment. The absorption bands in phosphate glasses are narrower and absorption coefficients higher than those in borate glasses. The esr spectrum of titanium(III) in all the glasses consists of a broad asymmetric line withg 1.94 in borate glasses, andg 1.92 in phosphate glasses; no hyperfine structure has been observed.     

Electron spin resonance spectra of Gd3+ ions in K2SO4-ZnSO4 glasses

Electron spin resonance (ESR) spectra of Gd³⁺ ions doped in K₂SO₄-ZnSO₄ glasses have been studied on an X-band ESR spectrometer at different temperatures (–120 to 150 C). The ESR spectrum at room temperature exhibits three prominent features with effectiveg-values of 5.6, 2.83 and 2.02. The spectra are similar to the U spectra familiar in many oxide and fluoride glasses, indicating very low and disordered site symmetries with a broad distribution of crystal fields. Remarkable changes have been observed in the spectrum with changes in the temperature, concentration and glass composition. The broadening of theg 2.02 line with increasing Gd³⁺ ion content indicates that the dipole-dipole interaction between the resonant centres increases with increase in Gd³⁺ ion content. A weak band at 36350cm^–1 is observed in the optical absorption spectrum of 0.5mol% Gd³⁺ in K₂SO₄-ZnSO₄ glass which has been assigned to the transition⁸S_7/2⁶P_7/2.     

Electronic and two-magnon light scattering in oxide superconducting crystals

From investigations of two-magnon Raman scattering (RS) under high pressures up to 430 kbar in Eu₂CuO₄ and YBa₂Cu₃O_6.2 crystals, it was shown that the dependence of the superexchange integralJ on the distance between Cu and O atoms in CuO₂ planesa is anomalously weak (Ja^–n, n=3±0.5). The large value ofJ indicates strong initial overlapping of Cu and O wave functions in high-T _c , materials. It was found that an increase in free carrier concentration results in a rapid increase of magnon damping and the disappearance of the two-magnon peak from RS spectra. A detailed study of electron Raman scattering has been carried out in superconducting and insulating YBa₂Cu₃O_6–x , single crystals. The spectral redistribution at frequencies<600 cm^–1 in different polarizations indicate that the superconducting gap is strongly anisotropic. In the normal (metallic) phase the behavior of the imaginary part of the response functionR() in the polarization (xx) corresponds to the model of a marginal Fermi liquid, and in the polarization (xx), this behavior is independent of the temperature. In insulating crystals,R() is independent of temperature toT200 K in both polarizations.     

63Cu NMR in the normal state of HgBa2Ca2Cu3O8+δ

We present a⁶³Cu NMR study of HgBa₂Ca₂Cu₃O₈₊ underdoped single crystals with T_c 115 K. While the uniform spin susceptibility decreases below T_o 370 K, relaxation rate measurements demonstrate the opening of a spingap at Q = (, ) below T* 230 K, the highest temperature reported so far. The characteristic energy of spin fluctuations is shown to be higher than in underdoped YBa₂Cu₃O_7–, and the analysis of the quadrupole and hyperfine couplings suggests that the in-plane Cu-O hybridization is also stronger. The T-dependence of T₁ is the same in the three CuO₂ planes which seems hardly compatible with the pure interlayer spin-pairing picture.     

Metastability of the K2NiF4 type structure of the solid solution LaCa(Cr x Al1−x )O4(0⩽x⩽0.10)

Metastability of the K₂NiF₄ type aluminate LaCaAlO₄ and its chromium diluted solid solution LaCaCr _x Al_1–x O₄ (x0.10) was evidenced at 1400C in air, in terms of demixing into the parent structures of the 11 intergrowth, i.e. the perovskite and rocksalt type LaAlO₃ (LaCr _x Al_1–x O₃) and CaO, respectively. This behaviour is discussed comparatively with YCaAlCO₄ and LaSrAlO₄ whose structures are stable under the same thermodynamic conditions. The results of a structure analysis are used to emphasize the role of the nine-fold co-ordination of the (A ³⁺=Y³⁺, La³⁺; A²⁺=Ca²⁺, Sr²⁺) cations as mixing the twelve-fold co-ordination of A ³⁺ in A ³⁺AlO₃ perovskite and the six-fold one of A ²⁺ in A ²⁺O rocksalt. Calcium-oxygen underbonding in the (La, Ca)-O-Al bridge is assumed to trigger the metastability of the intergrowth structure at high temperature.     

Electron paramagnetic resonance of Cu2+ and VO2+ ions in phosphate glasses

Electron spin resonance (ESR) spectra ofx(CuO · V₂O₅ (1 –x) (Na₂O · P₂O₅) andx(CuO · 2V₂O₅) (1 –x) (Na₂O · P₂O₅) glasses for 0 x 40 have been studied at the X-band and at 300 K. It is found that forx 5, both Cu²⁺ and VO²⁺ are present, mostly as isolated species. Forx 10, broad resonance lines atg = 2.1524 forx(CuO · V₂O₅) (1 –x) (Na₂O · P₂O₅) and atg = 2.1448 forx(CuO · 2V₂O₅) (1 –x) (Na₂O · P₂O₅) are observed which may be mainly due to dipole-dipole type interaction between transition metal (TM) ions. Spin Hamiltonian parameters of TM ions have been calculated. Optical spectra of the sodium phosphate glasses doped with single TM ions have also been studied. The theoretical optical basicity, A_th, of these doped glasses has been calculated. It is found that for VO²⁺ ionsg ,g and increase whileA ,P and g _|/g decrease with increase in A_th. However, no significant change is observed in the spin Hamiltonian parameters of Cu²⁺ with the change in A_th.     

Simulation of the Process of Water Freezing in a Round Pipe

The problem of freezing of pure water in a round pipe is treated with due regard for convection under asymmetric thermal boundary conditions in the absence of motion along the pipe. The problem is solved numerically using the control volume approach, SIMPLER algorithm, and the enthalpy method. Results are obtained for three Grashof (Gr) and six Biot (Bi) numbers: Gr = 1.55 × 10⁶, Bi = 0.305 (0 < ), Bi = 0.044 ( < 2); Gr = 1.24 × 10⁷, Bi = 0.610 (0 < ), Bi = 0.087 ( < 2); Gr = 9.89 × 10⁷, Bi = 1.220 (0 < ), Bi = 0.174 ( < 2). The correctness of calculation of the problem disregarding free-convection flows is analyzed.     

BCS temperature-dependent superconducting energy gap in domain boundaries of melt-textured YBa2Cu3O7

Attenuation and velocity measurements in low magnetic fields in the superconducting state of a melt-textured sample of YBa₂Cu₃O₇ are reported. Changes in both attenuation and relative velocitydv/v are observed at the penetration fieldH _c1 of its domain boundaries. The change indv/v atH _c1 appears to be proportional to the repulsive force between vortices. The change in atH _c1 may be produced by a relaxation process involving superconducting quasiparticles in the vicinity of the normal core of the vortices. Analysis of the relaxation time associated with this process yields a temperature-dependent energy gap which follows the BCS dependence. The relaxation time associated with the process is about 10^–11 sec.     

Tl-NMR Study on High–Tc Oxides TlM2CaCu2O7–δ(M=Ba, Sr) : Spin-Gap in Underdoped and Overdoped Systems

The Spin–lattice relaxation rate and the Knight shift have been measured for Tl–based cuprates TlBa ₂ CaCu ₂ O ₇₊ (TB1212) and TlSr ₂ Y _l–x Ca _x Cu ₂ O ₇₊ (TS1212). In the underdoped sample of TS1212 with Tc=34K. (T ₁ ) ^–1 showed a gap–like behavior from the temperature T _SG=120K. As for the slightly overdoped sample of TB1212 with T _c =80K, both the Knight shift and (T ₁ ) ^–1 showed a significant decrease from 160K, suggesting the existing of the spin-gap not only around q(, ) but also q0.     

A new series of mercury-based high-Tc superconductors (Hg, W)Sr2(Y1?x Cax)Cu2

A new series of superconducting mercury-based layered cuprates has been synthesized. X-ray diffraction indicates that the compounds with formula Hg_0.8W_0.2Sr₂Y_1–x Ca _x Cu₂O₆₊ (0.3x0.6) exhibit the 1212 structure with space groupP _4/mmm . The investigation of superconductivity determined by electrical resistance measurement shows that the superconducting transition temperature (T _c , onset) of Hg_0.8W_0.2Sr₂Y_0.4Ca_0.6Cu₂O₆₊ is up to 94 K.     

Quantum tunneling of vortices in single crystal Tl2CaBa2Cu2O8 superconductors

Data are presented on the temperature-dependent time-logarithmic magnetic relaxation rate S(T) = ¦dM/d_in t¦ of the high-T_c superconductor Tl₂CaBa₂ Cu₂O₈. It is found that at low temperatures the relaxation rate has the form S(T) = A(H) exp[(T/T^*)²], which does not extrapolate to zero at T = 0, thus excluding conventional thermally activated flux creep and providing evidence of quantum vortex tunneling. From a quantum flux tunneling theory, it is shown that S(T) I/_er _p ² . The measurements of the relaxation rate thus provide information about the effective viscosity _e of fluxons.