Spectroscopic investigations of Cu2+ in Li2O-Na2O-B2O3-Bi2O3 glasses

Pure and copper doped glasses with composition,x Li ₂ O-(40-x)Na ₂ O-50B ₂ O ₃-10Bi ₂ O ₃,have been prepared over the range 0 ≤ x ≤ 40. The electron paramagnetic resonance (EPR) spectra of Cu²⁺ ions of these glasses have been recorded in the X-band at room temperature. Spin Hamiltonian parameters have been calculated. The molecular bonding coefficients, α² and β², have been calculated by recording the optical absorption spectra in the wavelength range 200–1200 nm. It has been observed that the site symmetry around Cu²⁺ ions is tetragonally distorted octahedral. The density and glass transition temperature variation with alkali content shows non-linear behaviour. The IR studies show that the glassy system contains BO₃ and BO₄ units in the disordered manner.     

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.     

Spectroscopic and transport studies of Cu2+ ion doped in (40 —x)Li2O—xLiF—60Bi2O3 glasses

The preparation of (40-x)Li₂O-xLiF-60Bi₂O₃ glassy system and spectroscopic and transport studies of this system are reported. IR results show that this glass consists of [BiO₃] units and indicate formation of Bi-F bonds with the addition of LiF. From the ESR spectra of Cu²⁺ ion, the effectiveg values are found to vary slightly with increasing concentration of fluorine ion. The optical absorption peak corresponding to Cu²⁺ increased linearly with increasing concentration of LiF between 620 nm and 728 nm except at 2.5 mole% of LiF where its value is 729 nm. This peculiar behaviour is attributed to the varying structural coordination of fluorine as the concentration of lithium fluoride is increased. The ionic conductivity measurements indicate that the conduction is due to adiabatic hopping of polarons and the activation energies are found to be temperature and concentration dependent     

Preparation and characterization of Ag-added Bi1.84Pb0.4Sr2Ca2.2Cu3O10+x bulk tube conductors for cryogen free superconducting magnet

Bulk tube conductors of Bi _1.84 Pb _0.4 Sr ₂ Ca _2.2 Cu ₃ O _10+x with addition of silver varying from 0 to 25 wt% (not reported earlier) were systematically studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), electrical transport and a.c. susceptibility techniques. The tube conductors formed by cold isostatic pressing (CIP) of the powders obtained from spray drying method have been made successfully. It was found that Ag addition has not only affected the formation of the desired Bi-2223 phase and the microstructure of these large bulk tube samples thereby influencing on the critical current ( I _c ),it also reduces the contact resistance to minimize the cryogen losses. These variations have been found to be Ag content dependent. An optimized value of 10 wt% Ag has been found to produce the best quality tubes showing reproducible I _c value > 120 Amp at 77 K which is in general a requirement to energies of the cryogen free conventional/HTSC superconducting magnets below 20 K.     

On the study of phase formation and critical current density in superconducting MgB2

Superconducting bulk MgB₂ samples have been synthesized by employing sintering technique without using any additional process steps, generally undertaken in view of the substantial loss of magnesium, during heat treatment. Starting with Mg rich powders having different atomic ratios of Mg : B, as against the nominally required Mg : B = 1:2 ratio, we have obtained superconducting MgB₂ samples of different characteristics. The effect of excess Mg in the starting mixture and processing temperature on the phase-formation, transition temperature (T _C) and critical current density (J _C) have been investigated by electrical transport and a.c. susceptibility measurements. The X-ray diffraction and X-ray photoelectron spectroscopic analyses of MgB₂ bulk samples have been carried out to understand the role of excess Mg and the effect of processing temperature. It is established that MgB₂ samples with high critical current density can be synthesized from a Mg rich powder having Mg : B in 2:2 ratio, at temperatures around 790°C. Critical current density has been found to vary systematically with processing temperature.     

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.     

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.     

Uses of α-Fe2O3 and fly ash as solid adsorbents

Solid adsorbents have shown great promise for control of particulate and non-particulate matter and as gas sensing devices in recent times. In the present study, adsorption of environmental toxic pollutant such as lead ions on solid adsorbents viz. α-Fe₂O₃ and fly ash, are reported. Considerable adsorption was observed on fly ash when compared to α-Fe₂O₃ surface. These studies are characterized by employing solid state and solution studies.     

(La2/5Ba2/5Ca1/5)(Mn(2/5)-x Ni x Ti3/5)O3: Rietveld studies, dielectric and magnetic properties of new perovskite-related oxides

Oxides of the type (La_2/5Ba_2/5Ca_1/5)(Mn_(2/5)-x _Ni x _Ti3/5)O₃ (0 ≤ x ≤ 0.4) have been synthesized by the ceramic route. All the above oxides have been found to crystallize in the cubic perovskite structure. Rietveld refinement of the Ni-based oxide, (La_2/5Ba_2/5Ca_1/5)(Ni_2/5Ti_3/5)O₃ gave rise to a composition (La_0.44Ba_0.38Ca_0.18) (Ni_0.42Ti_0.58)O_2.85(6) and the refined lattice parameter obtained was 3.9411(2) Å (space group Pm3m;R(F²) = 0.026,R _p = 0.074,wR _p = 0.087). A shift from antiferromagnetic to paramagnetic behaviour is observed with increase in nickel concentration, the Mn-rich phases showing antiferromagnetism around 5 K. There is a systematic decrease in the dielectric constant, ε and loss tangent with increase in Ni concentration (from ε = 592 forx = 0 to ε = 78 forx = 0.4).     

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.     

Microstructural characterization in diffusion bonded TiC-Al2O3/Cr18-Ni8 joint with Ti interlayer

Ceramic matrix composite, TiC-Al₂O₂, and stainless steel, Cr18-Ni8, were joined at 1400 K by solid state diffusion bonding, making use of a Ti foil acting as thermal stress relief interlayer. The microstructure of the joint was thus formed. The diffusion bonded TiC-Al₂O₃/Cr18-Ni8 joint was investigated by a variety of characterization techniques such as scanning electron microscope (SEM) with energy dispersion spectroscopy (EDS) and X-ray diffraction (XRD). The results indicate that Ti foil is fully fused to react with elements from substrates and Ti₃Al, TiC and α-Ti are formed in the diffusion bonded TiC-Al₂O₃/Cr18-Ni8 joint. The interfacial shear strength is up to 99 MPa and the shear fracture occurs close to the ceramic matrix composite due to the application of Ti foil acting as thermal stress relief interlayer.     

Optical properties of a correlated electron system:V 2 O 3

The optical spectrum of V₂O₃ is found to resemble a Hubbard model system as described in an infinite-dimensional approximation. Assuming the validity of this comparison, we parameterize the effective Coulomb repulsive energy, the bandwith, and the mass enhancement. We suggest implicitly that these results should be compared with the cuprate and heavy Fermion superconductors.     

Optical absorption of nickel (II) in Na2O-NaCl-B2O3 and Na2O-NaBr-B2O3 glasses

The optical absorption spectra of nickel(II) have been studied in Na₂O-NaX-B₂O₃ glasses X = Cl or Br); the absorption bands have been interpreted in terms of Ligand Field Theory. In halide-free B₂O₃-rich glasses nickel(II) is octahedral, and halide substitution is accompanied by the formation of a tetrahedral nickel(II)-oxide-halide complex. In alkali-rich glasses nickel(II) is square planar and/or tetrahedral and no halide substitution can be observed. It is suggested that the halide ions are unable to substitute for oxygen in the predominantly covalent nickel(II)-oxygen bonds of the complex formed in basic glasses.     

Microstructural studies on variation of defect parameters in Zr-Sn alloys and their transition with interchange of solvent and solute in Zr-Ti and Ti-Zr alloy systems by modified Rietveld method and Warren-Averbach method

The effects of deformation and the transition of microstructural defect states with the interchange of solvent and solute in Ti-Zr and Zr-Ti alloys of six different compositions and Zr-Sn alloys in three different compositions have been investigated by X-ray diffraction line profile analysis. The detailed analysis of the X-ray powder diffraction line profiles was interpreted by Fourier line shape analysis using modified Rietveld method and Warren-Averbach method taking silicon as standard. Finally the microstructural parameters such as coherent domain size, microstrains within domains, faulting probability and dislocation density were evaluated from the analysis of X-ray powder diffraction data of Zr base Sn, Ti and Ti base Zr alloys by modified Rietveld powder structure refinement. This analysis confirms that the growth fault, β, is totally absent or negligibly present in Zr-Ti, Ti-Zr and Zr-Sn alloy systems, because the growth fault, β, has been observed to be either negative or very small for these alloy systems. This analysis also revealed that the deformation fault, α, has significant presence in titanium-base zirconium alloy systems but when zirconium content in the matrix goes on increasing beyond 50%, this faulting behaviour suffers a drastic transition and faulting tendency abruptly drops to a level of negligible presence or zero. This tendency has also been observed in Zr-Sn alloys signifying high stacking fault energy. Therefore, Zr and Zr-base alloys having high stacking fault energy can be used as hard alloys in nuclear technology at high temperature.     

Bulk thermal expansion studies of BiCaSrCu2O x and Bi2CaSr2Cu2O x

The compounds BiCaSrCu₂O _x and Bi₂CaSr₂Cu₂O _x were prepared by ceramic techniques and characterized by X-ray powder diffractometry (XRD) and microthermogravimetry (TG) and their bulk thermal expansion measurements were carried out using dilatometry in the temperature range 298T1073 K in air. The results have been analyzed and are compared with those obtained earlier for YBa₂Cu₃O₇. The XRD analysis shows that both BiCaSrCu₂O _x and Bi₂CaSr₂Cu₂O _x are single phase in nature, having an orthorhombic symmetry. The TG analysis carried out in oxygen, air, and nitrogen shows negligible weight loss (R~0.1%) on heating to 1073 K, indicating that these two compounds, unlike YBa₂Cu₃O₇, are quite stable. The analysis of bulk thermal expansion data reveals that the average linear thermal expansion coefficient ( ₁) for both BiCaSrCu₂O _x and Bi₂CaSr₂Cu₂O _x is almost the same ( ₁ 10.5×10^–6 K^–1) and is found to be nearly half of that for YBa₂Cu₃O₇ ( ₁ 18×10^–6 K^–1), suggesting that the interatomic bonding in both BiCaSrCu₂O _x and Bi₂CaSr₂Cu₂O _x is stronger as compared to YBa₂Cu₃O₇.