EPR and magnetic investigations of MnO-B2O3-PbO glasses

Electron paramagnetic resonance (EPR) of Mn²⁺ ions revealed their distribution on different structural units of a 2B₂O₃PbO glass matrix doped with MnO. Octahedral symmetric sites, tetragonally distorted, were detected. The progressive clustering of manganese ions was evidenced when the MnO content increased. EPR and magnetic susceptibility data revealed that both Mn²⁺ and Mn³⁺ ions are simultaneously present in the glass matrix and the transition from isolated ions in samples with x1 mol % to those involved in dipole–dipole interactions for samples with x30 mol % and antiferromagnetically coupled ions when x>30 mol %.     

EPR and magnetic susceptibility studies of xCr2O3-(1-x) 3B2O3-PbO glasses

By using X-ray diffraction analysis, EPR and magnetic measurements, the chromium-ion distribution in xCr₂O₃-(1–x) [3B₂O₃-PbO] glasses with 0x35 mol% Cr₂O₃ was studied. EPR investigation evidenced the presence of both Cr³⁺ and Cr⁵⁺ ions, the latter being in small proportion, in agreement with the atomic magnetic moment values. For concentrations x20 mol% Cr₂O₃ the isolated Cr³⁺ ions coexist with those coupled by super-exchange magnetic interactions, the isolated ones prevailing only for x<3 mol% Cr₂O₃. For x>20 mol % Cr₂O₃ microcrystalline precipitates were detected, giving rise to an antiferromagnetic transition with Néel temperature, N _N310 K and paramagnetic Curie temperature, _p=–480 K.     

Conduction mechanism at high electric field and switching phenomena in V2O5-P2O5 and V2O5-P2O5-TeO2 glasses

A previous investigation [1] suggests that the conduction in some vanadate glasses is ohmic up to a field of the order of 10⁵ V cm^–1 with an activation energy range from 0.31 to 0.48 eV depending on composition, but independent of temperature above room temperature. In this work the electrical conductivity of these glasses at high electric field is reported. The results suggest that above a field of 4×10⁵ V cm^–1 conduction becomes non-ohmic, and this is found to be due to lowering the potential barrier to the carrier at high electric field. Memory switching is observed in thin blown film samples of both binary and ternary glass systems, and is associated with field-induced crystallization of a localized region and the formation of a conduction channel in the switched area due to a self-heating effect.     

Optical absorption studies for TeO2-P2O5 and Bi2O3-TeO2-P2O5 glasses

A range of TeO₂-P₂O₅ and Bi₂O₃-TeO₂-P₂O₅ glass systems were prepared. The optical absorption spectra were measured in the spectral range 300–800 nm and it was found that the fundamental absorption of these glasses is dependent on the glass composition. The optical energy gap of binary glasses increases with increasing TeO₂ content while the addition of Bi₂O₃ to TeO₂-P₂O₅ decreases the optical energy gap. The absorption edges of these glasses arise from direct forbidden transitions and occur at photon energies in the range of 2.17 to 2.97 eV for TeO₂-P₂O₅ glasses and 2.63 to 2.32 eV for Bi₂O₃-TeO₂-P₂O₅ glasses depending on their composition.     

Preparation and properties of rapidly quenched glasses in the V2O5-PbO system

Rapidly quenched glassy films in the V₂O₅-PbO system were prepared using a twin-roller type apparatus. The glass formation region was 0–60 mol% PbO. The first crystallization temperature increased from 210 C for the V₂O₅ glass to 292 C for the glass of 60 mol% PbO. The metastable unknown phase was first crystallized in the glasses around 50 mol% PbO. Infrared absorption spectra of the glasses were measured. Electrical conductivity of the glasses decreased with increasing of PbO content. The electrical behaviour of the glasses is discussed based on the glass structure estimated from the infrared spectral data.     

Compositional dependence of infrared absorption spectra studies for TeO2-P2O5 and TeO2-P2O5-Bi2O3 glasses

The infrared absorption spectra of the vitreous TeO₂-P₂O₅ and Bi₂O₃-TeO₂-P₂O₅ systems are studied in the spectral region of 4000 to 200 cm^–1. Absorption bands in this range are assigned. The midband wavenumber and the absorption intensity for the attributed bands are found to be strongly and systematically dependent on glass composition. Quantitative analysis was also attempted to justify our attribution of the observed bands.     

Spectroscopic,electrical and EPR studies of binary semiconducting oxide glasses containing 50 mol% V2O5

Recent measurements on the V₂O₅-GeO₂ glass system consisting of an equimolar mixture of V₂O₅ and GeO₂ revealed that increase in electrical conductivity of these glasses upon annealing could be attributed to the increase in V⁴⁺ and V³⁺ content which accompanied the microstructure formation. In the present work we report a similar study on V₂O₅-TeO₂ and V₂O₅-P₂O₅ glass systems. It was found that in tellurite glass V³⁺ content increased upon annealing and V⁴⁺ content remained unchanged. In phosphate glass some increase in V⁴⁺ and no significant change in V³⁺ contents were observed. V³⁺ and V⁴⁺ contents in glasses could be best estimated from optical and electron paramagnetic resonance spectra, respectively.     

Effect of the addition of Fe2O3 and heat treatment duration on the magnetic susceptibility of V2O5-P2O5-B2O3 glass system

The effect of the addition of Fe₂O₃ and heat treatment duration on the magnetic susceptibility of vanadium borophosphate glass were studied. The magnetic susceptibility of glass samples was found to increase with increasing Fe₂O₃ content, which may be explained by the formation of the FeO₆ group and the change of Fe²⁺ to Fe³⁺ which has higher paramagnetic properties. No detectable changes in the magnetic susceptibility with heat treatment for the samples containing 0.0, 0.5 and 1.0 mol% Fe₂O₃ was observed. The magnetic susceptibility for the heat treated samples containing 2.5, 5.0 and 7.5 mol% Fe₂O₃ decreases sharply with increasing duration of heat treatment up to 6 h and then remains almost constant. The sharp decrease in magnetic susceptibility of 2.5 mol% Fe₂O₃ is attributed to the increase in the number of ferrous ions. The sharp decrease for samples containing 5.0 and 7.5 mol% Fe₂O₃ is attributed to the increase in the number of Fe³⁺ in tetrahedral co-ordination. The rate of crystallization owing to the heat treatment was calculated and was found to increase with increasing iron oxide content. The geometry of crystallization was found to be in three-, two-and one-dimension(s) for samples containing 2.5, 5.0 and 7.5 mol% Fe₂O₃, respectively.     

Structural studies of some V2O5-P2O5-B2O3-Fe2O3 glass systems

X-ray diffraction and infrared measurements were performed on vanadium borophosphate glass containing different amounts of iron ranging from 0–7.5 mol % and heat treated at 300 °C for various times. The structure and phase separation could be determined for each glass composition. V₂O₅ was the main precipitated phase in all heat-treated samples, and its amount was dependent on the heat-treatment time and Fe₂O₃ content. Also FeP was detected in samples heat treated for 24 h. The infrared measurements showed the presence of both V⁴⁺ and V⁵⁺. The symmetry of V₂O ₇ ⁴⁻ and VO ₄ ³⁻ groups was found to increase with increasing Fe₂O₃ content. It was also found that some PO₄ changed to BO₃, forming a non-bridging oxygen.     

Relaxation studies on V2O5-TeO2 glasses using heterogeneous conductor model

The dielectric modulus spectra of glasses in the system V₂O₅-TeO₂ have been studied as a function of frequency in the temperature range 230 to 330K. A heterogeneous conductor model developed recently with the assumption of a sinusoidally varying local conductivity in the conducting phase has been successfully applied to analyse the data in this glass system. The Kohlrausch-Williams-Watts (KWW) stretched exponential function has also been used to fit the measured modulus spectra. The exponentβ is found to be correlated to the conductivity fluctuation in the conducting phase as assumed in the heterogeneous model.     

Study of structures and properties of ZnO-Sb2O3-P2O5-Na2O glasses

The influence of ZnO substitution by 0–12 wt.% Na₂O on the properties of ZnO-Sb₂O₃-P₂O₅-Na₂O glasses has been investigated. The structure and properties of the glasses with the composition of (13.86-x)ZnO-57.93Sb₂O₃-28.21P₂O_5?x Na₂O (x = 0–12 wt.%) were characterized by infrared spectra (IR), X-ray diffraction and differential thermal analysis (DTA). The results of IR indicated an increase in the intensity of symmetric vibrations of P-O-P bond, which was confirmed by the improvement of water durability with the increasing amount of Na₂O in the range of 0–10 wt.%. Substitution of 10 wt.% Na₂O led to the weight loss of the glass to 5.93 mg/cm^?2 after immersion in deionized water at 50 °C for 24 h. The results of XRD showed that the ability of crystallization decreased, indicating the good thermal stability of the glass. The glass containing 8 wt.% Na₂O had the best properties in every respect and might be an alternative to lead based glasses for the applications, providing further composition improvement.     

The structure of glasses in the TeO2-P2O5 system

The co-effects of two glass-formers in the TeO₂-P₂O₅ system are studied on the basis of neutron diffraction data. The curves for the radial distribution function (RDF) obtained show a high extent of destruction of the short-range order in the tellurite matrix, while the basic co-ordination PO₄ polyhedron remains unchanged. The co-ordination number (cn) of the Te atom changes from 4 to 3+1 and marked tendency towards elongation of the Te-O distances over 2.3 Å is observed. The considerably higher stability of the PO₄ polyhedra and their strong influence on the TeO₄ polyhedra is established. The observed smearing effect of the Te-Te, Te-second O and O-second O distances in the range of 3.8 to 3.9 Å in other tellurite glasses is also characteristic of this system. A structural interpretation of the liquid-liquid immiscibility on the short-range order level in the system is given. A critical composition with 26±5% of the second glass-former is established, above which concentration a stable immiscibility in the tellurite systems is observed. An attempt is made to construct two adequate structural models (microhomogeneous and microheterogeneous) for the short-range order in the glasses studied.     

氧化物掺杂对钒磷铋系玻璃性能的影响

本研究制备了以V2O5、P2O5、B2O3为基体,掺杂Na2O、Li2O、CuO、Sb2O3、B2O3为辅助原料的低熔点钒磷铋系玻璃。研究了氧化物的添加对钒磷铋系玻璃的骨架网络结构、特征温度、热膨胀系数和化学稳定性的影响。实验结果表明:CuO的添加使钒磷铋系玻璃特征温度明显下降,而Na2O、Li2O、Sb2O3和B2O3的添加使钒磷铋系玻璃特征温度均有不同程度的上升。添加B2O3能够大幅度降低钒磷铋系玻璃的热膨胀系数。氧化物对钒磷铋系玻璃的耐水性影响程度为:CuO>B2O3>Sb2O3>Na2O>Li2O;耐酸性影响程度为:B2O3>CuO>Sb2O3>Na2O>Li2O;耐碱性的影响程度为:Sb2O3>Na2O>CuO>B2O3≈Li2O。配比为5%Na2O,5%Li2O,3.5%CuO,10%Sb2O3和5%B2O3制得的钒磷铋系玻璃,热膨胀系数更接近于氧化铝陶瓷基板,拥有较高的耐腐蚀性,能够用于电子浆料中。     

Electrical properties of V2O5-PbO-GeO2 glasses

Glasses in the V₂O₅-PbO-GeO₂ system containing 55 mol% V₂O₅ were found to undergo a droplet-type phase separation. The dispersed phase is rich in GeO₂. The volume percent of this phase increases with increasing GeO₂/PbO ratio in the glass. When the volume percent of dispersed phase is small, the direct current conductivity depends mainly on the continuous phase. When the dispersed phase reaches about 42 vol%, a second kind of phase separation appears in the continuous phase and thus alters the conductivity dramatically. Providing that the heterogeneity is taken into consideration, all the conductivities of phase-separated glasses can be explained by the theory proposed by Mott.     

ZnO-Al2O3-P2O5玻璃水化过程及机理的研究

研究了不同Al2O3/P2O3摩尔比和热历史的ZnO-Al2O3-P2O5玻璃在不同条件下的水化过程,利用XRD对部分水化过程的水化产物进行了晶相分析,探讨了其水化机理.结果表明:Al2O3/P2Os比的增加及退火均可降低ZnO-Al2O3-P2O5玻璃的水化速率;玻璃的水化累计失重量均与水化时间成线性关系,水失重百分数随着水化温度的提高,呈指数规律增加.研究认为:ZnO-Al2O3-P2O5玻璃的水化过程受表面水化层与内部未水化部分间的界面化学反应控制,水化过程中玻璃网络解体,相继生成了[P2O7]4-和白色不溶性物质Zn2P2O7·3H2O.     

Growth kinetics of spherulitic apatite in some MgO-CaO-SiO2-P2O5 glasses

Crystallization of glasses with compositions (wt%) of 11.2 MgO, 33.3 SiO₂, (55.5–x) CaO, and xP₂O₅ (x=18.3, 16.65, 15.825 and 15.0) resulted in a spherulitic apatite phase with different crystal morphologies. An ellipsoidal morphology was observed for x=18.3, 16.65 and 15.825, and an anomalous morphology was observed for x=15.0. A metastable phase, which was similar in some characteristics to apatite, was also found for x=15.0. The growth kinetics of the spherulitic apatite crystals were investigated to explain the above observations. Both the dendrite arms along the [0001] and [1 1¯20] directions of the apatite crystals showed constant growth rates in each glass. Growth-rate anisotropy was found between these two directions. The ellipsoidal shape of the apatite crystals is explained by this growth-rate anisotropy. The growth rates, and the growth-rate anisotropy, varied with the P₂O₅ content in such a manner that the changes in phase formation behaviour can be explained on the basis of the kinetic results.     

Preparation and characterization of binary V2O5-Bi2O3 glasses

Characterization of the binary V₂O₅-Bi₂O₃ glasses prepared by rapidly quenching the melt has been made from the studies of X-ray diffraction, scanning electron microscopy, infrared absorption, differential thermal analysis, electron paramagnetic resonance, chemical analysis, density and electrical properties. Stable glasses are obtained for 95 to 75 mol % V₂O₅ by quenching on a stainless steel substrate, while quenching on a copper substrate extends the glass formation range from 95 to 70 mol % V₂O₅. The V-O bond vibration in the glasses occurs at 1020 cm^–1 and the V^5% ion exists in six-fold coordination as in crystalline V₂O₅. All the glasses appear to be in single phase. The spin concentration in the glasses is found to be independent of temperature. A second heat-treatment at 255° C develops crystalline phase in the glasses. Unlike infrared absorption, electron paramagnetic resonance, density and chemical compositions, the electrical and thermal (DTA) properties are found to be slightly sensitive to the thermal history of preparation of the glasses. The high-temperature (300 to 500 K) conduction in the glasses seems to be due to adiabatic hopping of polarons. The thermopower is observed to be independent of temperature and provides evidence for small polaron formation in the glasses.