Optical and IR study of Li2O–CuO–P2O5 glasses

Infrared (IR) and UV spectra of ternary Li₂O–CuO–P₂O₅ glasses in two series Li₂O(65−X)%–CuO(X%)–P₂O₅(35%), X = 20, 30, 40 and Li₂O(55−X)%–CuO(X%)–P₂O₅(45%), X = (10, 20, 30) were studied. Infrared (IR) investigations showed the metaphosphate and pyrophosphate structures and with increase of CuO content in metaphosphate glass, the skeleton of metaphosphate chains is gradually broken into short phosphate groups such as pyrophosphate. IR spectra showed one band at about 1,220 and 1,260 cm⁻¹ for P₂O₅(35%) and P₂O₅(45%) series, respectively, assigned to P=O bonds. For CuO additions ≤20 mol%, the glasses exhibit two bands in the frequency range 780–720 cm⁻¹ which are attributed to the presence of two P–O–P bridges in metaphosphate chain. But for CuO addition ≥30 mol%, the glasses exhibit only a single band at 760 cm⁻¹ which is assigned to the P–O–P linkage in pyrophosphate group. In optical investigations, absorption coefficient versus photon energy showed three regions: low energy side, Urbach absorption, and high energy side. In Urbach’s region, absorption coefficient depends exponentially on the photon energy. At high energy region, optical gap was calculated and investigations showed indirect transition in compounds and decreases in optical gap with increases of copper oxides contents that is because of electronic transitions and increasing of nonbridging oxygen content.     

EPR and Magnetic Susceptibility of Na2O–CuO–P2O5 Glasses

Abstract

(50?x/2)Na₂O–xCuO–(50?x/2)P₂O₅ glasses (x=1, 5, 15, or 30 mol%) have been prepared and characterized by electron paramagnetic resonance (EPR) and magnetic susceptibility measurements. The shape of the Cu²⁺ EPR spectrum depends on the Cu content, and the corresponding computer simulations suggest that the Cu²⁺ ions occupy two different sites in these glasses: one of them is preponderant at low Cu content and the other is preponderant at high content, in which the Cu²⁺–Cu²⁺ interactions are more important. From EPR parameters, it was found that for the site at low content, the covalency of copper ion bonding with the surrounding ligands is appreciable. The magnetic susceptibility data appear to follow the Curie–Weiss law (χ=C/(T?θ_p)) with negative paramagnetic Curie temperature θ_p indicating antiferromagnetic interactions between Cu²⁺ ions that are more significant in the samples with high Cu content, in agreement with EPR results.     

Activation energy and conductivity of glasses in the P2O5–V2O5–Li2O system

The conductivity of glasses in the 50\textP_\text2 \textO_\text5 - x\textV_\text2 \textO_\text5 - ( 50 - x )\textLi_\text2 \textO50{\text{P}}_{\text{2}} {\text{O}}_{\text{5}} - x{\text{V}}_{\text{2}} {\text{O}}_{\text{5}} - \left( {50 - x} \right){\text{Li}}_{\text{2}} {\text{O}} system was studied as a function of temperature and composition. For all compositions, the conductivity variation as a function of temperature followed an Arrhenius type relationship. Isothermal variation of conductivity as a function of composition showed a minimum for a molar ratio x near 20. Probable mechanisms for decrease of conductivity with decrease of vanadium oxide concentration were explained. The minimum in room temperature was attributed to increase of V⁴⁺/V⁵⁺ with decrease of vanadium oxide in specific concentrations of vanadium oxide. Activation energy increased with decrease of V₂O₅ content. This behavior was attributed to increase of average spacing between vanadium ions.     

Crystallization and conductivity of 2CaO–La2O3–5P2O5 glass–ceramic with Al2O3 addition

Al₂O₃ was added to a 2CaO–La₂O₃–5P₂O₅ metaphosphate, to replace 10% of the Ca²⁺ ions by Al³⁺, forming a phosphate with the nominal composition 1.8CaO–0.1Al₂O₃–La₂O₃–5P₂O₅. The effect of Al₂O₃ addition and heat treatment on the microstructure and conductivity of the resulting glass–ceramics was investigated by XRD, SEM, TEM, and AC impedance spectroscopy. Upon transformation from glass to glass–ceramic, conductivities increased significantly. The glasses were isochronally transformed at 700 and at 800 °C for 1 h or 5 h, in air, following heating at 3 or 10 °C/min. With Al₂O₃ addition, after a heat treatment at 700 °C, 100–300 nm nano-domains of LaP₃O₉ crystallized from the glass matrix. Annealing at 800 °C produced a further order of magnitude conductivity increase for the Al-free glass, but less so for the Al-containing glass.     

Structure,dielectric and bioactivity of P2O5–CaO–Na2O–B2O3 bioactive glass

Bioactive phosphate glasses have been widely investigated for bone repair. Phosphate glass system of 47P₂O₅–30.5CaO–(22.5?x)Na₂O–xB₂O₃ has been prepared by melt quenching technique. From the Raman analysis, it is confirmed that phosphate network form metaphosphate structure. Bioactivity of the glass is studied by immersing the prepared glass in simulated body fluid (SBF). All the glasses exhibited bioactivity after soaking in SBF. Addition of B₂O₃ to the glass by replacing the Na₂O produces considerable effect on the dielectric and bioactivity of the glass. Ion dynamics are also analyzed through imaginary modulus and imaginary dielectric permittivity.     

Photoluminescence and Photoacoustic Spectroscopies of Fe3+ in the LiGa5O8–LiGaSiO4–Li5GaSi2O8 System

This report is devoted to the study of the low and room temperature photoluminescence and photoacoustic spectroscopy of the Fe³⁺ impurity ion in the LiGa₅O₈–LiGaSiO₄–Li₅GaSi₂O₈ system. The sample was obtained by solid-state reaction between β-Ga₂O₃, Li₂CO₃, SiO₂ and appropriated quantities of Fe₂O₃. It was investigated by X-ray diffraction to determine the formed phases and through photoluminescence, excitation and photoacoustic spectroscopy measurements. The broad absorption and emission bands in the visible and near-infrared spectral regions presented by that system constitute the motivation for this study. More specifically, the luminescence occurs over a large interval of wavelengths, between 400 nm and 800 nm.     

Theory of metal–insulator transition in PrFe4P12 and PrRu4P12

We derive all symmetry allowed couplings between Fe/Ru or P ion displacements and the Pr ion 4f² ground state doublet in PrFe₄P₁₂ and PrRu₄P₁₂. A (1,1,−2)-type distortion of the Fe/Ru positions splits the 4f² doublet into non-magnetic eigenstates with opposite quadrupole moments. The sign of both the distortion and the quadrupole moment alternate from site to site, resulting in anti-quadrupolar ordering. A (1,1,1)-type distortion does not lift the degeneracy of the 4f² doublet. Either distortion may also open a gap at the Fermi surface, causing a metal–insulator transition in PrRu₄P₁₂ and a partial metal–insulator transition in PrFe₄P₁₂.     

High-Temperature Heat Capacity of Germanates Pr2Ge2O7 and Nd2Ge2O7 within 350–1000 K

Pr2Ge2O7 and Nd2Ge2O7 were obtained via solid-phase synthesis from Pr2O3 (Nd2O3) and GeO2 with multistage firing in air within 1273–1473 K. A temperature effect on molar heat capacity of the oxide compounds was measured with a differential scanning calorimetry. Their thermodynamic properties were calculated from the C _P = f(T) dependences.

     

Birefringence in YA1O3∶Nd between 2–4·7 eV

The paper presents original spectra of the birefringence of the orthorhombic YAlO₃Nd single crystal in the region from 2 to 4·7 eV, describes a reflection method of null ellipsometry which was used for the measurement of the spectra and, in conclusion, makes a comparison between the measured spectra and the values predicted from the values measured over the region of lower energies 1·1 – 2·2 eV.The authors are grateful to J. Kvapil for samples preparation.     

Synthesis and Magnetic Properties of the Core–Shell Fe3O4/CoFe2O4 Nanoparticles

Physics of the Solid State - The Fe3O4/CoFe2O4 nanoparticles with a core–shell structure with an average size of 5 nm have been obtained by codeposition from the iron and cobalt chloride...     

Ultrasonic,FTIR and thermal investigations of SiO2–Na2O–CaO–P2O5 glasses doped with CeO2

The longitudinal and shear ultrasonic wave velocities for different compositions of SiO₂–Na₂O–CaO–P₂O₅ glasses were measured at room temperature (305 K) using a pulse-echo method at a frequency of 4 MHz. The elastic moduli, Poisson's ratio, microhardness, Debye temperature and other ultrasonic parameters were obtained from experimental data and analyzed using bond compression theory. By calculating the number of network bonds per unit volume, the average stretching constant, and the average ring size, information about the structure of the glass can be deduced. Structural changes after doping with CeO₂ were investigated by FTIR spectroscopy, and by measurements of the thermal expansion coefficient, glass transition and softening temperature to throw more light on the characterization of these glasses.     

Proton conductivity in sol–gel-derived P2O5–TiO2–SiO2 glasses

The sol–gel method was applied to prepare the P₂O₅–TiO₂–SiO₂ glasses with high proton conductivities and chemical stability. The glasses were prepared by the reaction of the Ti- and Si-alkoxides with PO(OCH₃)₃ or H₃PO₄, followed by heating at 600 °C. The obtained glasses were porous, the average pore diameter of which was <2 and 4 nm for glasses prepared using PO(OCH₃)₃ and H₃PO₄, respectively. The phosphorous ions, occurring as PO(OH)₃ in the TiO₂-free glass, were polymerized with one or two bridging-oxygen ions per PO₄ unit with the increasing TiO₂ content. Despite the P₂O₅–SiO₂ binary glasses exhibiting high conductivities of ∼10⁻² S/cm at room temperature, they also dissolved after immersing for 24 h in water. The chemical stability of these glasses increased significantly on the addition of TiO₂.     

Optical properties of glasses in the Li2O–MoO3–P2O5 system

Glasses xLi₂O–(50-x)(MoO₃)₂–50P₂O₅ with x = 10, 20, 30, and 40 mol% were prepared and their optical and electrical properties were investigated. Analysis of the IR spectra revealed that the Li⁺ ions act as a glass modifier that enter the glass network by breaking up other linkages and creating non-bridging oxygens in the network. The optical absorption edge of the glasses was measured for specimens in the form of thin blown films and the optical absorption spectra of those were recorded in the range 200–800 nm. From the optical absorption edges studies, the optical band gap (E _opt) and the Urbach energy (E _e) values have been evaluated by following the available semi-empirical theories. The linear variation of (αhν)^1/2 with hν, is taken as evidence of indirect interband transitions. The E _opt values were found to decrease with increasing Li₂O content by causing increase in the number of non-bridging oxygens in network. The Urbach tail analysis gives the width of localized states between 0.48 and 0.74 eV.     

Mid-infrared laser-induced grating experiments of C2H4 and NH3 from 0.1–2 MPa and 300–800 K

Laser-induced thermal gratings (LITG) were generated in mixtures of ethylene and ammonia in nitrogen using mid-infrared laser radiation from a grating-tuned, low-pressure, pulsed (5 ms pulse width) CO₂ laser, and read out with a continuous wave Nd:YLF laser. The LITG signal intensity was measured as a function of pressure (0.1–2 MPa) and temperature (300–800 K, at 0.1 and 1 MPa) by tuning the laser to the accidental coincidences of the 10P(14) and 10R(6) emission lines with molecular absorption transitions of C₂H₄ and NH₃, respectively. Comparisons are made with theoretical predictions for the grating efficiency from a simple thermalization model. A theoretical comparison of the temporal LITG signal response for three excitation pulse shapes – a delta function, a realistic pulse, and a square wave is presented. Furthermore, it is shown that for NH₃, most of the decrease of the LITG signal intensity with increasing temperature is due to the corresponding decrease in fractional molecular absorption of the pump beam radiation. The diagnostic capabilities of the mid-infrared LITG experiment is demonstrated for spatially resolved ethylene measurements with long laser pulses in a premixed stoichiometric CH₄–air flame at atmospheric pressure. Received: 17 March 2000 / Revised version: 23 March 2000 / Published online: 13 September 2000     

Microstructure and varistor properties of ZnO–V2O5–MnO2 ceramics with Ta2O5 addition

The effect of Ta₂O₅ addition on microstructure, electrical properties, and dielectric characteristics of the quaternary ZnO–V₂O₅–MnO₂ vaistor ceramics was investigated. Analysis of the microstructure indicated that the quaternary ZnO–V₂O₅–MnO₂–Ta₂O₅ ceramics consisted of mainly ZnO grain and minor secondary phases such as Zn₃(VO₄)₂, ZnV₂O₄, TaVO₅, and Ta₂O₅. As the amount of Ta₂O₅ increased, the sintered density increased from 94.8 to 97.2% of the theoretical density (5.78 g/cm³ for ZnO), whereas the average grain size decreased from 7.7 to 6.0 μm. The ceramics added with 0.05 mol% Ta₂O₅ exhibited the highest breakdown field (2715 V/cm) and the highest nonlinear coefficient (20). However, further increase caused α to abruptly decrease. The Ta₂O₅ acted as a donor due to the increase of electron concentration in accordance with the amount of Ta₂O₅. The donor concentration increased from 1.97×10¹⁸ to 3.04×10¹⁸cm^?3 with increasing the amount of Ta₂O₅ and the barrier height exhibited the maximum value (0.95 eV) at 0.05 mol% Ta₂O₅.     

E.P.R. study of γ-irradiated single crystals of K2C2O4.H2O and (NH4)2C2O4.H2O

The electron paramagnetic resonance of γ-irradiated single crystals of K₂C₂O₄.H₂O and (NH₄)₂C₂O₄.H₂O has been studied. The spectra show interesting microwave power saturation effects. The singlet spectrum is attributed to the C₂O₄ ^- radical derived from the C₂O₄ ^-- ion. The principal g-values are determined to be 1·998, 2·0028 and 2·0004. Certain weak lines are observed with different power saturation and interpreted as due to OH radicals derived from water molecules in the crystal lattice.