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.     

BaO-SiO2-B2O3-TiO2系统玻璃的电子自旋共振研究

采用电子自旋共振(ESR)方法研究了钛在BaO-SiO2-B2O3-TiO2系统玻璃中的价态及Ti3+的结构状态.结果表明:在正常空气气氛下熔制的玻璃中,钛主要以Ti4+形式存在,所产生的顺磁信号归因于玻璃的本征缺陷和熔制时TiO2中氧的逸出而形成的氧空位捕获电子引起,且随温度升高,氧空位浓度减少;在微还原性气氛下,有部分Ti3+形成,出现g┃=1.9954,g┸=1.9823两处顺磁峰,它们对温度有着不同的依从性,即随温度升高:g┃ 峰增强,g┸峰降低;根据Ti3+的g┃ 、g┸)参数的性质,认为Ti3+是处于带四方畸变的八面体配位场中,形成[TiO6];即便在液氮温度下,也难以观察到Ti3+的超精细结构谱线.     

Optical absorption and electron spin resonance studies of Cu2+ in Li2O-Na2O-B2O3-As2O3 glasses

The local structure around Cu²⁺ ion has been examined by means of electron spin resonance and optical absorption measurements in xLi₂O-(40-x)Na₂O-50B₂O₃-10As₂O₃ glasses. The site symmetry around Cu²⁺ ions is tetragonally distorted octahedral. The ground state of Cu²⁺ isd _x ²−y ².The glass exhibited broad absorption band near infrared region and small absorption band around 548 nm, which was assigned to the ²B_1g →²E_g transition.     

Crystallization and properties of CaO-P2O2-B2O3 glasses

Glasses were prepared with compositions (50–0.5 x) CaO.(50–0.5 x) P₂O₅ · x B₂O₃ with B₂O₃ contents (x) from 0 to 45 mol%. The glass transformation temperature (T _g), dilatational softening temperature (T _D) and Vickers hardness (H _V) initially increased with x, but showed maxima at about x=20 for T _g and T _D and at about x=35 for H _V. The thermal expansion coefficient decreased with x, levelling off at about 35 mol% B₂O₃. The maximum tendency to crystallize occurred at around 25 mol% B₂O₃. Volume nucleation (and hence glass-ceramic formation) and surface nucleation were obtained for x between 15 and 25 mol%. The first phase to appear was BPO₄, which was probably homogeneously nucleated. Subsequently the 4CaO · P₂O₅ phase was heterogeneously nucleated on the BPO₄. For 10 x 35 only surface nucleation was observed. The kinetics of nucleation were investigated in the 20 mol% B₂O₃ glass. The changes in properties and crystallisation behaviour with B₂O₃ content were related to short-range structural information. Infrared spectra and literature data indicated a threedimensional network of B-O-B and B-O-P linkages in the glasses.     

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.     

Electron spin resonance study in P2O5-MoO3 and P2O5-MoO3-CaO glasses

ESR spectra of the glass systems P₂O₅-MoO₃ and P₂O₅-MoO₃-CaO are presented. The electron spin resonance results showed a strongly exchange-narrowed interaction with the [Mo⁵⁺]/[Mo⁶⁺] ratio and line shapes independent of temperature over the range 77 to 300 K. This result supports the concept of temperature-dependent mobility of the carriers and an unchanged paramagnetic site over this temperature range. The more important difference between the spectra of the binary and ternary glasses is that in the former with an increase in MoO₃ content the concentration of Mo⁵⁺ ions decreases but in ternary glasses it is reversed, i.e. the ion concentration of Mo⁵⁺ increases with increase in MoO₃ content.     

D.c. conductivity and hopping mechanism in Bi2O3-B2O3 glasses

The physical and transport properties of semiconducting glasses are highly interesting, providing useful information regarding the structure and conduction mechanism, respectively. The physical and transport properties such as density, number of ions per unit volume, hopping distance, polaron radius, d,c. conductivity and activation energy are reported. Similarly the hopping conduction mechanism is examined. The physical property (density) is used to determine the probable structure of the glass sample. The small polaron hopping model is applied to the glass system. The methods of examining the hopping conduction mechanism are discussed in the light of the small polaron model. The methods suggested by Holstein and by Sayer and Mansingh are applied to the determination of adiabatic or non-adiabatic hopping conduction. It was observed that in this system adiabatic hopping conduction is present.     

Electron microscopy and EDX-microanalysis of photochromic silver halide glasses of the composition systems Al2O3-B2O3-SiO2 and Na2O-CaO-SiO2

The microstructure and microanalysis study of two glasses containing AgCl precipitated particles have been carried out by transmission electron microscopy (TEM, replica method), scanning electron microscopy (SEM) and SEM/EDX (energy dispersive X-ray spectrometry). The composition of these glasses doped with silver halide and CuO was formulated from the Al₂O₃-B₂O₃-SiO₂ and Na₂O-CaO-SiO₂ systems respectively. In both glasses the seeds, nuclei, crystals and matrix were analysed, and the mean size and number of crystals were evaluated from the TEM and SEM observations. The microstructure in both glasses is different because of the different shape of the silver halide particles; the particles of the Al₂O₃-B₂O₃-SiO₂ glass are rounded while Na₂O-CaO-SiO₂ shows square precipitated particles. Likewise, the darkening behaviour is basically different; the Al₂O₃-B₂O₃-SiO₂ glass shows a higher darkening velocity than the Na₂O-CaO-SiO₂ glass, showing for this glass a very small slope value.     

Electron paramagnetic resonance of some ABX3 compounds

Electron paramagnetic resonance studies of NaMnCl₃, KMnCl₃, KCuCl₃, NH₄CuCl₃ were made between 400 and 5 K. The peak-to-peak derivative linewidths of these substances were found to be 14, 70, 10 and 5 mT, respectively. The line splitting below 15 K in NaMnCl₃ was attributed to hyperfine interaction with the Mn²⁺ nucleus. The g values and the peak-to-peak derivative linewidths of KMnCl₃, KCuCl₃ and NH₄CuCl₃ were found to be temperature independent within the limits of experimental errors. The g values of NaMnCl₃ and KMnCl₃ are isotropic, however, of KCuCl₃ and NH₄CuCl₃ are slightly anisotropic at room temperature and their principal values were determined. Hyperfineless structure of the spectra and the broad linewidths seem to be mainly due to exchange interactions of Mn²⁺ and Cu²⁺ ions among themselves in the respective compounds.     

Glass transition temperature of glasses in the SiO2-Na2O-CaO-P2O5-Al2O3-B2O3 system

A total of 24 glasses in or near the bioactive region in the system SiO₂-Na₂O-CaO-P₂O₅-Al₂O₃-B₂O₃ were studied. By differential thermal analysis their glass transition temperatures,T _g, were determined. On basis of an experimental plan for 16 glasses, two phenomenological equations describing the relationship betweenT _g and glass composition were developed. The equations describeT _g within the compositional ranges: SiO₂, 38.0–65.5 Na₂O, 15.0–30.0; CaO, 10.0–25.0; P₂O₅, 0–8.0; B₂O₃, 0–3.0; Al₂O₃, 0–3.0 wt%. The glass transition temperature shows a linear dependence of the Na₂O content. The higher the Na₂O content, the lower theT _g. Compositional alterations not including Na₂O influencesT _g little in comparison with changes in the Na₂O content.     

Acoustic investigations on PbO-Al2O3-B2O3 glasses doped with certain rare earth ions

Elastic moduli (Y, η), Poisson’s ratio (σ), microhardness (H) and some thermodynamical parameters such as Debye temperature (θ_D), diffusion constant (D _i),latent heat of melting (ΔH _m) etc of PbO-Al₂O₃-B₂O₃ glasses doped with rare earth ions viz. Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺ and Yb³⁺, are studied as functions of temperatures (in the temperature range 30–200°C) by ultrasonic techniques. All these parameters are found to increase with increasing atomic numberZ of the rare earth ions and found to decrease with increasing temperature of measurement. From these results (together with IR spectra of these glasses), an attempt is made to throw some light on the mechanical strength of these glasses.