Effect of barium titanate on the unit cell parameter of Nd0·5 Li0·5TiO3

Structural characteristics of new type of perovskites with formula Ba _x (Nd_0·5Li_0·5)_1−x TiO₃ (0⩽x⩽1) are reported. Nd_0·5Li_0·5TiO₃ crystallises with orthorhombic distorted perovskite structure, while Ba _x (Nd_0·5Li_0·5)_1−x TiO₃ crystallises with tetragonal distorted perovskite structure.     

Dielectric, elastic, anelastic and conductivity behaviour of ferroelectromagnetic composites, Ni0·5Zn0·5Fe1·95O4?δ + Ba0·8Pb0·2TiO3

Ferroelectromagnetic composites with compositions, X Ni_0·5Zn_0·5Fe_1·95O_4−δ + (1 − X) Ba_0·8Pb_0·2TiO₃, in which X varies as 0, 0·005, 0·010, 0·015, 0·020, 0·040, 0·060, 0·080 and 1 in mole %, were prepared by conventional ceramic double sintering process. The presence of two phases was confirmed by X-ray diffraction. The temperature variation of dielectric constant, ɛ′, dielectric loss, tan δ, d.c. conductivity, a.c. conductivity, elastic and anelastic behaviour of ferrite-ferroelectric composites were studied in the temperature range 30–350°C. The a.c. conductivity measurements on these composites in the frequency range 100 Hz-1 MHz at room temperature reveal that the conduction mechanism is due to small polaron hopping. The dielectric and elastic data were discussed in the light of phase transitions.     

An analysis of the electrical conductivity in BaSO4-added Ag2SO4 solid electrolyte system

The compositions (1 −x)Ag₂SO₄−(x)BaSO₄, wherex=0·01 to 0·6, were prepared by slow cooling of the melt. The extent of the solid solubility of Ba²⁺ in Ag₂SO₄ was determined by X-ray powder diffraction and scanning electron microscopy. The bulk conductivity of each sample was obtained using a detailed impedance analysis. The partial substitution of Ba²⁺ results in the enhancement of conductivity in compliance with the classical aliovalent doping theory. A simplistic model based on lattice distortion (expansion) due to partial substitution of Ag⁺ by the bigger Ba²⁺ has been considered to explain enhanced conductivity. Beyond solid-solubility limit (5·27 mole%) the BaSO₄-dispersed Ag₂SO₄ conductivity follows the usual trend seen in binary systems. An increase in conductivity in this case is discussed in the light of interfacial reactions and surface defect chemistry. The maximum conductivity in 20 mole% BaSO₄ dispersed Ag₂SO₄ is due to percolation threshold.     

Ion-selective properties of metastable (VO)<Subscript>0.09</Subscript>V<Subscript>0.18</Subscript>Mo<Subscript>0.82</Subscript>O<Subscript>3</Subscript> · 0.54H<Subscript>2</Subscript>O

This paper describes a thin-film solid electrode with an ion-sensitive membrane based on the mixed oxide (VO)_0.09V_0.18Mo_0.82O₃ · 0.54H₂O. The electrode is selective for tetravalent vanadium in the concentration range 3 ≤ pC _V ⁴⁺ ≤ 5 and acidity range 4.5 ≤ pH ≤ 6, with a slope close to the theoretical value. In the range 1 ≤ pH < 5, the electrode responds to changes in hydrogen ion concentration, with a slope of 50 ± 2 mV/pH. Its alkali-metal-ion response shows up in the range 1 ≤ pC _M ⁺ ≤ 4 for pH ≥ 6. We examine the effect of the Li⁺, K⁺, Na⁺, Cs⁺, Rb⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Co²⁺, Ni²⁺, Mn²⁺, Al³⁺, Cr³⁺, and VO₂⁺ ions on the potential of the electrode and determine its selectivity coefficients for these cations.     

Thermoelectric power in Gd3+-substituted Cu-Cd ferrites

Polycrystalline Cd _x Cu_1−x Fe_2−y Gd _y O₄ ferrites fory=0·0 and 0·1 were prepared by ceramic technique. X-ray diffractograms of powder samples show cubic symmetry withx⩾0·2 fory=0·0 and 0·1, while compositions withx=0·0 fory = 0·0 and 0·1 are tetragonal. The thermopower measurements for Gd³⁺-undoped ferrites in the temperature range 300 K to 788 K shown-type conductivity forx⩾0·2. The substitution of Gd³⁺ changedn-type conductivity of the compositions top-type. The mobilities calculated show decreasing trend on Gd³⁺ substitution. The values of activation energy ΔE and drift mobilityE _d suggest polaron formation in substituted samples. The conduction mechanism is explained on the basis of localized model and formation of Gd³⁺+Fe²⁺ stable pairs at B site and Cu¹⁺+Fe³⁺ at A site.     

Synthesis and characterization of Eu3+ activated hexagonal ABaGd(PO4)2 (A+=Li, Na, or K) phosphates

BaGd_0·5(PO₄)₂: Eu _0·5 ³⁺ and ABaGd_0·5(PO₄)₂: Eu _0·5 ³⁺ (where A⁺=Li, Na or K) double phosphates were synthesized by solid state diffusion method. These powders were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. XRD results showed many distinct lines in the XRD spectra. SEM measurement showed grains of different sizes in double phosphates. The Eu³⁺-ion emission lines for⁵ D ₀→⁷ F _j (j=1, 2, 3, and 4) transitions showed a splitting into 3, 2, 1, and 2 components, respectively. Strength of these lines was enhanced by the addition of alkali ion to BaGd_0·5(PO₄)₂: Eu _0·5 ³⁺ double phosphate. However, as the alkali ion varied from Li⁺ to K⁺, the intensity of⁵ D ₀→⁷ F ₂ line (617 nm) in the red region increased at the cost of⁵ D ₀→⁷ F ₁ line (599 nm) in the orange region. Suitable explanation has been proposed for this phenomena.     

Superconductivity in compound Y1-2x Ce x Ba2+x Cu3O6·5+δ system

Partial substitution of Ce in place of Y has been achieved by taking care of charge compensation and compounds with the general formula Y_1-2 xCe_xBa₂₊ xCu₃O_6·5+δ have been successfully prepared. X-ray powder diffraction analysis reveals that this substitution gives orthorhombic single phase for 0⩽x⩽0·3. TheT _c remains nearly unchanged between 94-90 K.     

Ion-selective properties of nanostructured alkali-metal-doped vanadium oxide

We have studied thin-film electrodes based on nanoparticulate vanadium oxide doped with alkalimetal cations. The hydrogen function of the electrodes manifests itself in the pH range 2–5, with a slope of 55, 54, and 54 ± 2 mV/pH for M _x V₂O₅·nH₂O with M = Li, Na, and K, respectively. Their sensitivity range is 10⁻⁴ to 10⁻¹ mol/l. The electrode potential as a function of concentration follows the Nernst equation with a slope of 55, 55, and 57 ± 2 mV/pC for M = Li, Na, and K, respectively. The Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ selectivity coefficients of the electrodes are determined.     

Studies on the spin-state equilibria of cobalt ions in the system La1−x Na x Co1−x Nb x O3 (x⩽0·40)

The spin-state equilibria of cobalt ions in the system La_1−x Na _x Co_1−x Nb _x O₃ (x⩽0·40) has been studied by measuring its magnetic susceptibility as a function of temperature in the range 300–600 K. It is found that the behaviour of the samples withx⩽0·10 is similar to that of LaCoO₃, while compositions withx⩾0·20 behave quite differently, exhibiting simple paramagnetic behaviour.     

Preparation and characterization of Ca1 −x La x Ti1 −x Co x O3 (0·00<x⩽0·50) system

The possibility of the formation of solid solution in the system Ca_{1 −x} La _x Ti_{1 −x} Co _x O₃ forx⩽0·5 has been investigated. X-ray diffraction studies show that compositions withx=0·05, 0·1, 0·2, 0·3 and 0·5 prepared by the ceramic method are single-phase materials. All the compositions have a structure similar to CaTiO₃ with a pseudo-cubic unit cell. Preliminary studies show that interfacial polarization contributes significantly to their dielectric constant.     

Magnetization and initial permeability studies of Nd3+ substituted Zn-Mg ferrite system

Polycrystalline ferrites, Zn _x Mg_1−x Fe_2−y Nd _y O₄ (x=0·00, 0·20, 0·40, 0·60, 0·80 and 1·00;y=0·00, 0·05 and 0·10), were prepared by standard ceramic method. The compositions, on characterization by X-ray diffraction, showed formation of single phase cubic spinels. Magnetic study of the compositions showed increase in magnetic moment,nβ, with Zn²⁺ concentration up tox=0·4 and a decrease thereafter. This was attributed to the existence of canted spin. The compositions forx=0·8 and 1·0 showed paramagnetic behaviour at and above room temperature. The substitution of Nd³⁺ ion caused reduction in the magnetic moment and Curie temperatures. Substituted Nd³⁺ ion showed its occupancy on octahedral (B) site. The dependence of the initial permeability was studied in the temperature range 298 K-700 K. This μ_i-T curve reflects the positive temperature coefficient of initial permeability for the compositionsx≤0·4 andy=0·00. On substitution of Nd³⁺ ion (i.e.y=0·05 and 0·10), the μ_i-T curves flatten, showing almost temperature independence of initial permeability. This is explained by positive contribution to the anisotropy constant,K ₁, by substituted rare-earth, Nd³⁺ ion.     

Dielectric measurements in vanadium doped barium titanate

Ceramic samples of Li_0·1Ba_0·95(V _x Ti_1−x )O₃, wherex=0 to 0·2 were prepared by solid state reaction method. The samples were characterized by XRD. The dielectric measurements have been carried out on the sintered disks as a function of the frequency (100 Hz-1 MHz) and temperature (300–420 K). The variation of dielectric constant with temperature indicates a diffuse phase transition in all the samples studied.     

Effect of praseodymium substitution on the growth and properties of Y1−x Pr x Ba2Cu3O7−δ (o <x < 0·4) single crystals

In the present paper, a modified self-flux technique has been successfully employed for the growth of pure and praseodymium substituted (partially) large single crystals of high temperature superconducting Y_1−x Pr _x Ba₂Cu₃O_7−δ (x = 0·0,0·2,0·4). Typical sizes of the platy and bulky crystals of pure YBCO(123) material are ≈ 2 × 2 × 0·1 mm³ and 4 × 1 × 1 mm³, respectively. In case of Pr-substitution, the typical sizes of platy and bulky crystals of Y_0·8Pr_0·2Ba₂Cu₃O_7−δ and Y_0·6Pr_0·4Ba₂Cu₃O_7−δ materials are ≈ 2 × 3 × 0·1 mm³ and 5 × 1 × 1 mm³ and ≈ 1 × 1·5 × 0·1 mm³ and 7 × 0·2 × 0·1 mm³, respectively. The morphology and growth habit of the as-grown single crystals and the critical transition temperature (T _c) of the oxygenated crystals were found to depend on the Pr-content. Paper presented at the poster session of MRSI AGM VI, Kharagpur, 1995     

Effect of calcium substitution on superconductivity and hole concentration in La1·5Ba1·5Cu3O z

The superconducting properties of single phase La_1·5−x Ca _x+y Ba_1·5−y Cu₃O _z , 0·0≤x≤0·60 (LC) and 0·0≤y≤0·70 (CB), compounds with tetragonal triple-perovskite structure are studied, using X-ray diffraction for their resistivity, a.c. susceptibility, and oxygen-content. La_1·5−x Ca _x Ba_1·5Cu₃O _z (LC) samples, 0·15≤x≤0·60, are superconducting withT _c ^R=0 between 40 and 74 K. With the increase inx, the oxygen content, hole concentration in the CuO₂ layers as well as theT _c increase. It is interesting to find that although the hole concentration and oxygen stoichiometry of the LaCa_0·5+y Ba_1·5−y Cu₃O _z (CB) compounds increase with the increase iny, theT _c ^R=0 remains nearly constant around 74 K fory=0·0−0·70. A correlation exists between theT _c and the hole concentration for LC and CB compounds.     

Effect of Al3+-substitution on the electrical and magnetic properties of Ni1·05Sn0·05Fe1·9O4 ferrites

The effect of Al³⁺-substitution on d.c. resistivity, dielectric constant, initial permeability, saturation magnetization and Curie temperature has been studied for Ni_1·05Sn_0·05Al _x Fe_1·9−x O₄ ferrites, whereinx varies from 0 to 0·5 in steps of 0·1. The d.c. resistivity increases slowly forx⩽0·3 followed by a rapid increase forx>0·3. The variation is explained on the basis of Verwey hopping as well as polaron hopping mechanisms, and the dilution effect of Al³⁺ ions. The behaviour of dielectric constant is attributed to interfacial polarization and follows the Koops model. The saturation magnetization and the Curie temperature decrease continuously with increasing Al³⁺ content and are explained using the concepts of sublattice magnetization and exchange interactions. The decrease in initial permeability is attributed primarily to decrease in saturation magnetization. The dispersions in initial permeability and magnetic loss tangent are also discussed.     

Electrical conduction in the solid solution La1 −x Na x Co1 −x Nb x O3 (0·01 ⩽x ⩽ 0·99)

Seebeck coefficient and DC resistivity of the solid solution La_{1 −x} Na _x Co_{1 −x} Nb _x O₃ (0·01 ⩽x ⩽ 0·99) have been measured in the temperature range 300–900 K. Seebeck coefficient is positive for all compositions over the temperature range of measurements. Conduction is due to 3d electrons of cobalt ions in the compositions withx ⩽ 0·60. Conduction occurs among localized sites for compositions withx ⩾ 0·70.     

Influence of Ce3+ on dielectric properties of tungsten bronze structured PBN ceramics

The effect of A-site substitution of Ce³⁺ in tungsten bronze structured PBN ceramics with the general formula, Pb_{(x − 3y/2)}Ce _y Ba_(1 − x)Nb₂O₆ and the stoichiometric chemical formula, Pb_{(0.65 − 3y/2)}Ce _y Ba_0.35Nb₂O₆, where y = 0, 2, 4, 6, 8 and 10 mol% ceramic compositions synthesized through solid state reaction method are reported. The X-ray diffraction studies exhibited the presence of an orthorhombic phase, and its intensity increased with the increasing Ce³⁺ content up to y = 6 mol% or A₃ composition. The lattice parameters, unit cell volume and density as a function of Ce³⁺ concentration are discussed. It is observed that increasing Ce³⁺ content in A-site influenced the dielectric properties. The optimum dielectric properties of room temperature dielectric constant (ε_RT) and dielectric maximum () are observed in y = 6 mol% or A₃ composition while Curie temperature (T _c) and dielectric loss (tan δ) constantly decreased from undoped to y = 10 mol%, and thus A₃ composition or 6 mol% Ce modified tungsten bronze structured-PBN could be suitable for capacitor applications.     

Effect of low level substitution of Sr–Ba on transport and magnetic behaviour of La<Subscript>0·67</Subscript>Ca<Subscript>0·33</Subscript>MnO<Subscript>3</Subscript>

In this paper we report the investigation of transition metal oxide compound, La_0·67Ca_0·25Sr_0·04Ba_0·04MnO₃ (LCSBMO), along with La_0·67Ca_0·33MnO₃ (LCMO), synthesized by sol–gel route under identical conditions. The effect of simultaneous low level substitution of large size ions such as Sr²⁺ and Ba^2 + for Ca^2 + ions on the electronic transport and magnetic susceptibility properties are analysed and compared apart from microstructure and lattice parameters. The temperature dependent electrical transport of the polycrystalline pellets of LCSBMO and LCMO when obeying the well studied law, r = r₀ + r₂   T²\rho = \rho_{0} + \rho_{2} \;T^{2} for T < T _MI , is observed to differ by more than 50% from the values of ρ ₀ and ρ ₂, with the former compound showing enhanced electrical conductivity than the latter. Similarly in fitting the adiabatic small polaron model for resistivity data of both the samples for T > T _MI , the polaron activation energy is found to differ by about 11%. In addition, the temperature dependent a.c. magnetic susceptibility study of the compounds shows a shift of about 6% in the paramagnetic to ferromagnetic transition temperature (285 K for LCSBMO and 270 K for LCMO).     

Structural and piezoelectric properties of barium-modified lead-free (K0.455Li0.045Na0.5)(Nb0.9Ta0.1)O3 ceramics

Ferroelectric (K_0.455Li_0.045Na_0.5)(Nb_0.9Ta_0.1)O₃ + x mol% BaCO₃ ceramic compositions with Ba²⁺ as an A-site dopant in the range of x = 0–1.2 mol% were synthesized by conventional ceramic processing route. Effect of Ba²⁺ content on the microstructure, ferroelectric, dielectric, and piezoelectric properties of the ceramics was investigated. The results of X-ray diffraction reveal that Ba²⁺ diffuse into the (K_0.455Li_0.045Na_0.5)(Nb_0.9Ta_0.1)O₃ lattices to form a solid solution with a perovskite structure having typical orthorhombic symmetry. As Ba²⁺ content increases, cell volume and tetragonality increase in the crystal structure of the ceramics. Increasing doping level of Ba²⁺ inhibits grain growth in the ceramics and reduces both the Curie temperature (T _c) and tetragonal–orthorhombic phase transition temperature (T _o-t). The bulk density, remnant polarization P _r, room-temperature dielectric constant (ε′_RT), planar electromechanical coupling factor k _p , and piezoelectric charge coefficient d ₃₃ are found to increase as Ba²⁺ concentration increases from 0 to 0.8 mol% and then decrease as Ba²⁺ content increases further from 0.8 to 1.2 mol%. High piezoelectric properties of d ₃₃ = 187 pC/N and k _p  = 48 % are found in 0.8 mol% Ba²⁺ composition. Optimum amount of Ba²⁺ dopant takes the polymorphic phase boundary region consisting of orthorhombic and tetragonal crystal structures of the ceramic system near the room temperature and enhances its piezoelectric properties.     

Dielectric and piezoelectric properties of Pb(Ni1/3Nb2/3)O3–PbTiO3–PbZrO3 ceramics modified with bismuth and zinc substitutions

The dielectric and piezoelectric properties of the (Pb_0.985Bi_0.01)(Ni_1/4Zn_1/12Nb_2/3)_x- (Zr_σTi_1-σ)_1-xO₃ piezoelectric ceramic system (0.2 ≤ x ≤ 0.7, 0.1 ≤ σ ≤ 0.9) were systematically investigated. The results showed that, after poling, the dielectric constant, ε ₃₃ ^T , increased for the tetragonal compositions but decreased for the rhombohedral compositions. Furthermore, high values of ε ₃₃ ^T and piezoelectric modulus, d ₃₁ were found for the compositions along the extension of the morphotropic phase boundary. The highest values of the planar electromechanical coupling factor, K _p, and the piezoelectric modulus, d ₃₁, were found to be 0.70 and − 274 × 10^-12 C N^-1, respectively. The Curie temperature, remanent polarization, coercive field and the lattice constants of the a and c axes in relation to the Pb(Ni_1/3Nb_2/3)O₃ content and the Zr/Zr + Ti ratio were also determined. This revised version was published online in November 2006 with corrections to the Cover Date.