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.     

Clustering of silver atoms in hydrogenated silver–sodium exchanged glasses

The diffusional growth regime of silver clusters in hydrogenated silver–sodium exchanged glasses has been numerically analysed. The diffusion coefficients of the three elements that contribute to silver cluster formation, namely H, Ag⁺, and Ag⁰, have been established. The activation energy of the reactant Ag⁰ diffusion coefficient is consistent in the three analysed different experimental results: Ag loss through evaporation, near-surface Ag accumulation, and optical absorption density. The calculated Ag⁰ diffusion coefficient accounts for the threshold time necessary to obtain a cluster size to give rise to a detectable absorption. Received: 27 September 1999 / Accepted: 11 October 1999 / Published online: 8 March 2000     

Structure–property correlations in lead silicate glasses and crystalline phases

Lead silicate glasses containing 40–65?mol% of PbO were prepared at two melt-quenching rates and characterized by X-ray diffraction, UV-Visible absorption spectroscopy, density, microhardness, thermo-mechanical analysis, differential scanning calorimetry and Raman scattering studies. On increasing the PbO concentration, density increases, glass transition temperature decreases and the optical absorption edge shifts towards longer wavelength. An intense optical absorption band was observed just below the absorption edge in glasses with 55?mol% and higher concentration of PbO. Dilatometric measurements show an unusual property that glasses do not show any abrupt increase in volume near the glass transition temperature but transform directly into the liquid state. Raman spectroscopy confirmed that the concentration of SiO₄ tetrahedra containing one or more NBOs increase with PbO mol%. Devitrification studies on lead silicate glasses found that samples with 40–45?mol% of PbO do not crystallize, whereas samples with higher PbO concentration produce multiple crystalline phases like PbSiO₃, Pb₃₃Si₂₄O₈₁, Pb₂SiO₄ and Pb₃Si₂O₇ on heat treatment.     

Formation of sub-surface silver nanoparticles in silver-doped sodium–lead–germanate glass

The formation of silver nanoparticles in 60GeO₂–20PbO–20Na₂O bulk glass doped with 0.15 wt% of Ag has been studied by optical methods in the near ultraviolet-to-near infrared and mid-infrared ranges. A clear optical absorption band, which grows when increasing the annealing temperature, is observed around 460 nm, as a consequence of the surface plasmon resonance in the Ag nanoparticles. From the simultaneous analysis of optical transmittance and spectroscopic ellipsometry spectra in the near ultraviolet-to-near infrared range, it is demonstrated that the nanoparticles are surprisingly formed only in a thin layer (some tens of nm thick) underneath the sample surfaces. The potential of such a simultaneous optical analysis for determining the localization of the nanoparticles in glasses of any nature is underlined. Based on the results of a complementary mid-infrared spectroscopy characterization, the processes involved in silver migration to the surfaces and further aggregation to form nanoparticles are discussed.     

High pressure studies on the electrical resistivity of Ge–Te–Tl glasses

The variation of electrical resistivity in the system of glasses Ge₁₇Te_83?xTl_x, with (1≤x≤13), has been studied as a function of high pressure for pressures up to 10 GPa. It is found that the normalized electrical resistivity decreases continuously with the increase in pressure and shows a sudden drop at a particular pressure (transition pressure), indicating the presence of a transition from semiconductor to near-metallic at these pressures which are in the range 3.0–5.0 GPa. This transition pressure is seen to decrease with the increase in the percentage content of thallium due to increasing metallicity of the thallium. The transition is reversible under application of pressure and X-ray diffraction of samples recovered after pressurization show that they remain amorphous after undergoing a pressurization decompression cycle.     

Adsorption of sodium ions and hydrated sodium ions on a hydrophobic graphite surface via cation-π interactions

Using density functional theory computation, we show that sodium ions and hydrated sodium ions can be strongly adsorbed onto a hydrophobic graphite surface via cation-π interactions. The key to this cation-π interaction is the coupling of the delocalized π states of graphite and the empty orbitals of sodium ions. This finding implies that the property of the graphite surface is extremely dependent on the existence of the ions on the surface, suggesting that the hydrophobic property of the graphite surface may be affected by the existence of the sodium ions.     

Novel photosensitive properties of gadolinium–lead germanate glasses

Glasses of the system xGd₂O₃ · (100 ? x)[7GeO₂ · 3PbO] with 0 ≤ x ≤ 40 mol% were prepared using the melt quenching method. Lead germanate glasses are particularly interesting in the context of the germanate anomaly. In this paper, we investigate changes in the coordination number of germanium in gadolinium–lead germanate glasses using molar volume analysis, density measurements, FTIR and UV–VIS spectroscopy, and density functional theory (DFT). Despite some inconsistencies, the coordination change model remains the currently accepted model for the anomalous behaviour of lead germanate glasses. Based on these experimental results, we propose the following mechanism for the germanate anomaly. (i) The low thermodynamic stability of the [GeO₆] structural unit and the occupation of interstices of larger dimensions (the six-coordinated interstices of the [PbO₆] structural units) in the lead germanate network yield [GeO₅] structural units with higher thermodynamic stability and larger ionic radii. (ii) Not linked to the terminal oxygens of the [GeO₅] structural units and with the formation of smaller network cavities of the lead germanate glass, links are required with [GeO₄] tetrahedra for stabilization, generating the formation of three-membered rings of [GeO₄] tetrahedral structural units.     

Ultrasonic and FT-IR studies on Bi2O3–Er2O3–PbO glasses

Glasses in the 90Bi₂O₃–(10?x)Er₂O₃?xPbO (x = 3, 5, 7, 9 and 10 mol%) system have been prepared by the melt-quenching technique. Elastic properties and FT-IR spectroscopic studies have been employed to study the role of PbO in the structure of the investigated system. Elastic properties and Debye temperature were recorded using sound wave velocity measurements at 4 MHz at room temperature. The results showed that density increased and molar volume decreased, while both sound velocities increased with an increase in x. Infrared spectra of the glasses revealed that the bismuthate network is affected by an increase in PbO content. The results are interpreted in terms of the conversion of [BiO₆] into [BiO₃] structural units, indicating that Pb ions have been substituted for erbium ions as tetrahedral network formers. The elastic moduli increased with increasing PbO content due to the increased average bond strength and degree of connectivity, as a direct effect of the increase in [BiO₃] structural units.     

Spectroscopic studies on Li2O–MgO–Bi2O3–B2O3 glasses

MgO-Li₂O-Bi₂O₃-B₂O₃ glasses were prepared by melt quench technique and analyzed with the help of refractive index, optical, IR, and Raman spectroscopy studies. The present glasses exhibited the mixed modifier effect (MME) through refractive index change non-linearly. The variation in the indirect optical band gap and band tailing in MgO content have been discussed with the glass structure. Based on the obtained values of α_o2-, optical basicity, and interaction parameters, the present glasses were termed as very semi covalent acidic oxide glasses. Raman and Infrared spectra reveal that these glasses are built up of BO₃, BO₄ units of B₂O₃ and octahedral [BiO₆], pyramidal [BiO₃] units of Bi₂O₃ were observed.     

Optical transitions in Er^3＋ doped lead germanate glasses

Er^{3+}- and Er^{3+}/Yb^{3+}-doped lead germanate glasses that are suitable for use in fibre lasers and optical amplifiers as well as optical waveguide devices have been fabricated and characterized. The absorption spectra from near-infrared to visible were obtained and the Judd－Ofelt parameters were determined from the absorption band. Intense and broad 1.53μm infrared fluorescence and visible upconversion luminescence were observed under 976 nm diode laser excitation. For 1.53μm emission band, the full widths at half-maximum are 36, 37, 51 nm for GPE, GPYE and GPFE samples, respectively. For frequency upconversion emission, the intense bands centred at around 524, 545, 657nm are due to the {}^4S_{3/2}+{}^2H_{11/2}→{}^4I_{15/2} and {}^4F_{9/2}→{}^4I_{15/2} transitions of Er^{3+} ions. The quadratic dependence of the green and red emissions on excitation power indicates that the two-photon absorption process occurs under the 976nm excitation.     

X-ray standing wave studies of metal ions incorporation in Langmuir–Blodgett films

The molecular organization in Langmuir–Blodgett films of phospholipids and metallomesogen deposited on silicon has been studied by the X-ray standing-wave method at the synchrotron radiation source BESSY (Germany). Analysis of the experimental data obtained made it possible to determine the composition of the organic multilayer nanosystems and localize the position of metal ions incorporated in organic layers from the aqueous subphase during film deposition.     

Interdiffusion in lithium–lead melts

Interdiffusion in lithium-lead melts containing 10.0, 15.0, 18.1, 20.0, 25.1, 30.2, 38.2, 40.1, 43.1, 46.7, 50.2, 60.2, and 70.0 at. % Pb was investigated using gamma-ray attenuation technique in the temperature range from 720 to 1030 K. It has been found that the concentration dependence of the interdiffusion coefficient has a maximum in the vicinity of 20 at. % Pb. This phenomenon is shown to relate to a tendency of formation of short-range order in liquid alloys of lithium?lead.     

Modifications induced by swift heavy ions in rapidly solidified Sn–8.5Sb–5.5Cu alloy

Alloys of composition Sn–8.5Sb–5.5Cu (in atomic percent) were rapidly solidified by a melt-spinning technique. The samples were irradiated at room temperature with GeV uranium ions of fluences between 9×10⁸ and 9×10¹¹ ions cm^?2. X-ray diffraction analysis revealed the formation of a new-phase Cu₁₁Sb₃ as well as a reduction in the axial ratio (c/a) of the matrix (β -Sn) indicating the regular re-arrangement of atoms. Scanning force microscopy showed no surface topographic changes with the ion fluence. The mechanical properties (Young's modulus and hardness) of the irradiated alloys were studied as a function of ion fluence. The radiation-annealing process is discussed in terms of the evolution of both resistivity and hardness as a function of ion fluence.     

Measurements of magnetostriction of paramagnetic Fe–Mo–Cu–B metallic glasses

Magnetostriction of amorphous Fe₇₉Mo₈Cu₁B₁₂, (Fe₁₂Co₁)₇₉Mo₈Cu₁B₁₂ and (Fe₉Co₁)₇₉Mo₈Cu₁B₁₂ prepared by planar flow casting was measured using a direct method. The results indicate that magnetostriction in parallel (_λ∥)$({\lambda }_{\parallel })$ and perpendicular (_λ⊥)$({\lambda }_{\perp })$ directions of applied magnetic field is linearly dependent on magnetic field. In order to determine the influences of chemical composition and the conditions of sample preparation the magnetostriction of pure BCC-Fe, Cu and Mo were also measured. Samples containing Co with Curie temperatures slightly above room temperatures were shown to exhibit a hybrid magnetostriction behaviour with both ferromagnetic and paramagnetic features.     

Structure,thermal behavior,and chemical durability of lead–calcium–phosphate glasses

ABSTRACT

Structure and physical properties of 25CaO–xPbO–(75–x)P₂O₅ (0≤x≤35) glasses are investigated in this paper. Substitution of PbO for P₂O₅ in the binary 25CaO–75P₂O₅ glass was found to increase the density and to decrease the molar volume. Fourier transform infrared (FTIR) and Raman spectroscopies show the evolution of the phosphate skeleton when the PbO content increases: Q³ to Q² species (0<x≤25) and Q² phosphate network (x = 25) to short phosphate groups (x > 25) such as (P₄O₁₃^6?) (x = 35). The glass transition temperature first decreases with x, then increases for x values larger than 10%. The evolution of the glass transition temperatures is interpreted from the structural data: the minimum point observed in T_g is attributed to the transition of the ultraphosphate network from the network containing the modifying cations at isolated sites to a network with modifier sub-structure sharing terminal oxygens. At higher PbO content, the large increase in T_g is due to the reticulation of the phosphate network by PbO₄ groups.     

Analytical studies on the Benney–Luke equation in mathematical physics

The enhanced (G′/G)-expansion method presents wide applicability to handling nonlinear wave equations. In this article, we find the new exact traveling wave solutions of the Benney–Luke equation by using the enhanced (G′/G)-expansion method. This method is a useful, reliable, and concise method to easily solve the nonlinear evaluation equations (NLEEs). The traveling wave solutions have expressed in term of the hyperbolic and trigonometric functions. We also have plotted the 2D and 3D graphics of some analytical solutions obtained in this paper.     

Giant magnetoresistance in Cu–Co films electrodeposited on n-Si

High quality Cu–Co alloy films with excellent metallic luster have been electrolytically deposited directly onto n-Si (1 0 0) substrate, thereby eliminating the need of a conducting seed layer, which is otherwise required when the films were grown on insulating substrates (Al₂O₃). The as-deposited Cu–Co films exhibit relatively higher magnetoresistance (MR) in comparison with the as-deposited films on Al₂O₃ under identical conditions. The observed increase in MR could be attributed to the reduced substrate current shunting. The MR further improves to 2.67% (at H=10 kOe) with vacuum annealing (at 425°C for 30 min) of the films on Si. This has been ascribed to the separation of Cu and Co phases resulting in a magnetic granular nanostructure. This value of MR of annealed films on Si is, however, lower in comparison with the value obtained for annealed films deposited on Al₂O₃. Glancing angle X-ray diffraction (GAXRD) has revealed the formation of copper silicide in these samples, which is responsible for the lower value of MR. Thus we have observed good MR with a copper silicide host matrix.     

Optical and luminescence properties of Dy3+ ions in K–Sr–Al phosphate glasses for yellow laser applications

Trivalent dysprosium (Dy³⁺)-doped K–Sr–Al phosphate glasses have been prepared and investigated for their optical and luminescence properties. Judd–Ofelt theory has been used to derive radiative properties for the ⁴F_9/2 level of Dy³⁺ ions. The luminescence spectrum of 1.0 mol% Dy₂O₃-doped glass shows intense yellow emission around 572 nm ascribed to ⁴F_9/2 → ⁶H_13/2 transition with 78 % branching ratio and emission cross section of the order of 2.48 × 10^?21 cm². Moreover, the quantum efficiency of the ⁴F_9/2 level has been found to be 76 %. The luminescence decay curves for the yellow emission (⁴F_9/2 → ⁶H_13/2) have been measured and analyzed as a function of Dy³⁺ ion concentration. The results revealed that Dy³⁺-doped phosphate glasses could be useful for yellow laser applications.     

The effect of Cu on precipitation in Al–Mg–Si alloys

TEM investigations of two alloys isothermally heat treated at 175°C and 260°C show how Cu additions to the Al–Mg–Si system affect precipitation. Both alloys had a solute content Mg?+?Si?=?1.3 at.%, 0.127 at.% Cu, but with Mg/Si 0.8 and 1.25. Cu-containing Guinier-Preston (GP) zones and three types of Q′ precursors are identified as most common phases at peak-hardness conditions, whereas β″ accounts for maximum 30% of the total number of precipitates. The precursors have needle (L and S precipitates) or plate (C precipitate) morphologies. They consist of different arrangements of Al, Mg and Cu atoms on a grid defined by triangularly arranged Si planes parallel with and having the same period as {100} Al planes. The Si grid is composed of nearly hexagonal sub-cells of a?=?b?=?4.05?Å, c?=?4.05?Å. The Cu arrangement on the grid is often disordered in the needle precursors. The plate precursor is ordered, with a monoclinic unit cell of a?=?10.32?Å, b?=?8.1?Å, c?=?4.05?Å, γ?=?101°.