Dielectric dispersion in Li2O–MoO3–B2O3 glass system doped with V2O5

Li₂O–MoO₃–B₂O₃ glasses containing different amounts of V₂O₅, ranging from 0 to 1.5 mol%, were prepared. The dielectric properties (viz., constant ′, loss tan δ, AC conductivity σ_ac over a wide range of frequency and temperature) have been studied as a function of the concentration of vanadium ions. The variation of AC conductivity with the concentration of V₂O₅ passes through a maximum at 0.8 mol% V₂O₅. In the high-temperature region, the AC conduction seems to be connected with the mixed conduction, viz., electronic and ionic conduction. The dielectric relaxation effects exhibited by these glasses have been analyzed quantitatively by pseudo Cole–Cole plot method and the spreading of relaxation times has been established. Further analysis of these results has been carried out with the aid of the data on ESR, IR and optical absorption spectra.     

Structure and crystallization kinetics of a Cu50Zr45Ti5 glassy alloy

The crystallization kinetics and structure changes in a melt-spun Cu₅₀Zr₄₅Ti₅ glassy alloy on heating were investigated by X-ray diffractometry, transmission electron microscopy, differential scanning calorimetry and differential isothermal calorimetry. The glassy phase in the Cu₅₀Zr₄₅Ti₅ alloy was crystallized forming Cu₁₀Zr₇ and CuZr₂ phases upon thermal annealing. The activation energy for crystallization obtained by the Arrhenius equation was 435 kJ/mol. The crystallization process took place by nucleation and growth mechanism, and an Avrami exponent of about 3.3 may indicate a three-dimensional interface-controlled growth of nuclei with a decreasing nucleation rate.     

Spectroscopic and dielectric studies on MnO doped PbO–Nb2O5–P2O5 glass system

PbO–Nb₂O₅–P₂O₅ glasses containing different concentrations of MnO ranging from 0 to 2.5 mol% were prepared. A number of studies viz., differential thermal analysis, infrared, optical absorption, luminescence, Raman and ESR spectra, magnetic susceptibility and dielectric properties (constant ′, loss tan δ, ac conductivity σ_ac over a range of frequency and temperature) of these glasses have been carried out. The results have been analyzed in the light of different oxidation states of manganese ions. The analysis indicates that when the concentration of MnO is around 1.0 mol%, manganese ions mostly exist in Mn²⁺ state, occupy network forming positions with MnO₄ structural units and increase the rigidity of the glass network. When MnO is present in higher concentrations, these ions seem to exist mostly in Mn³⁺ state and occupy modifying positions.     

Induced crystallization and physical properties of Li2O–CaF2–P2O5:TiO2 glass system: Part I. Characterization, spectroscopic and elastic properties

Li₂O–CaF₂–P₂O₅ glasses mixed with different concentrations of TiO₂ (ranging from 0 to 0.8 mol%) were crystallized at 500 °C. The samples are characterized by X-ray diffraction, scanning electron microscopy and differential thermal analysis techniques. Spectroscopic properties (IR and Raman) and elastic properties (viz., Young's modulus E, shear modulus G and micro-hardness H) at room temperature are studied. The X-ray diffraction and the scanning electron microscopic studies revealed the presence of lithium phosphate, lithium titanium phosphate and titanium phosphate crystal phases. The differential thermal analysis traces of these samples exhibit three crystalline temperatures. The IR and Raman spectra of these samples have exhibited bands due to TiO₄ and TiO₆ structural units in addition to the conventional bands due to various phosphate structural groups. The analysis of these results indicated that the sample crystallized with 0.6 mol% of TiO₂ possesses the highest density, high mechanical strength and more compact network.     

Subsolidus phase relations of the ZnO–Li2O–P2O5 system

As a systematic search for suitable flux to grow zinc oxide single crystals, the subsolidus phase relations of the ternary system ZnO–Li₂O–P₂O₅ were investigated by means of X-ray diffraction (XRD). There are 6 binary compounds, 5 ternary compounds and 17 three-phase regions in this system. A new compound, Li₆Zn(P₂O₇)₂, is found in this system based on XRD experiments. The phase diagrams of the pseudo-binary systems Li₃PO₄–ZnO and LiZnPO₄–ZnO are investigated. It shows that the compounds, Li₃PO₄ and LiZnPO₄, are not suitable as flux for the growth of ZnO single crystals below 1250 °C.     

Fluorescence and Judd–Ofelt analysis of Nd doped P2O5–Na2O–K2O glass

Sodium potassium phosphate glass consisting different Nd₂O₃ concentrations have been prepared to study the effect of Nd³⁺ concentration on optical absorption and fluorescence properties. From the absorption spectra, Racah (E¹, E², E³), spin-orbit (ξ_4f) and configuration interaction (α) parameters are calculated and reported for all the Nd³⁺ doped glasses. Judd–Ofelt intensity parameters (Ω₂, Ω₄, Ω₆) are evaluated and these parameters are used to study the covalency as a function of Nd³⁺ concentration. Results show that covalency decreases with the increase of Nd³⁺ concentration. By using these three intensity parameters, total radiative transition probabilities (A_T), radiative lifetimes (τ_R), branching ratios (β) and integrated absorption cross-sections (Σ) have been computed for certain excited states of Nd³⁺ in these mixed alkali phosphate glasses for all the concentrations. From the fluorescence spectra, peak stimulated emission cross-sections (σ_p) have been calculated for the two transitions, ⁴G_7/2 → ⁴I_13/2 and ⁴G_7/2 → ⁴I_11/2 of Nd³⁺ in all these glass matrices. From the absorption spectra, the optical band gaps (E_opt) for both direct and indirect transitions have been obtained. All these spectroscopic parameters are compared for different Nd³⁺ concentrations. From these studies, a few transitions are identified for laser excitation among various transitions.     

Role of titanium valence states in optical and electronic features of PbO–Sb2O3–B2O3:TiO2 glass alloys

PbO–Sb₂O₃–B₂O₃ glasses mixed with different concentrations of TiO₂ (ranging from 0 to 1.5 mol.%) were synthesized. The samples are characterized by X-ray diffraction, scanning electron microscopy and DSC techniques. A variety of properties, i.e. optical absorption, photoluminescence, infrared, ESR spectra, magnetic susceptibility, photo-induced birefringence (PIB) and dielectric properties (constant ′, loss tan δ, a.c. conductivity σ_ac over a wide range of frequency and temperature) of these glass–ceramics have been explored. The analysis of these results indicated that Ti ion surrounding ligands play principal role in the observed PIB and the sample crystallized with 0.8 mol.% of TiO₂ is the most suitable for the applications in non-linear optical devices.     

Induced crystallization and physical properties of Li2O–CaF2–P2O5:TiO2 glass system: Part II. Electrical, magnetic and optical properties

The results of various physical properties namely, dielectric properties (dielectric constant, loss tan δ, ac conductivity σ, over a wide range of frequency and temperature and dielectric breakdown strength in air medium at room temperature), optical absorption, electron spin resonance (ESR) at liquid nitrogen temperature and magnetic susceptibility at room temperature of Li₂O–CaF₂–P₂O₅:TiO₂ glass-ceramics have been reported. The optical absorption and magnetic susceptibility studies indicated that the titanium ions exist in Ti³⁺ state in addition to Ti⁴⁺ state in these samples. However, the reduction seems to be the lowest in the sample containing 0.6 mol% of TiO_2. The dielectric constant and loss variation with the concentration of TiO₂ have been explained on the basis of space charge polarization mechanism. The dielectric relaxation effects exhibited by these samples have been analyzed by a pseudo Cole–Cole plot method and the spreading of dielectric relaxation has been observed. The ac conductivity in the high temperature region seems to be related both with electronic and ionic movements. The low temperature (or the nearly temperature independent) part of conductivity could be explained on the basis of quantum mechanical tunneling model. The studies on dielectric breakdown strength indicated the highest insulating strength for the sample containing 0.6 mol% of TiO₂.     

Optical and thermal properties of P2O5-Na2O-CaO-Al2O3:CoO glasses doped with transition metals

The aim of this paper is to report the optical and thermal properties of V₂O₅ and CuO doped P₂O₅-Na₂O-CaO-Al₂O₃:CoO glasses so as to investigate their possible use in solar collection applications. The optical absorption spectra of the glasses at room temperature were in the spectral range of 200-1100 nm. The optical band gaps of the glass samples were determined for direct and indirect transitions. When transition metal ions doped to the base glass, the optical band gap decreased. Changes in the refractive indices vs. wavelength for all the specimens were also examined by spectroscopic ellipsometry. By measuring the heat capacities and thermal diffusion coefficients of the specimens at varying temperatures, their thermal conductivities were calculated to be in the 320-620 K temperature range. The obtained glasses seem to be promising materials and can be used in solar collector applications.     

Subsolidus phase relation in the system ZnO–Li2O–MoO3

The subsolidus phase relation of the system ZnO–Li₂O–MoO₃ has been investigated by X-ray diffraction (XRD) analyses. The phase diagram has been constructed. There are six binary compounds and one ternary compound in this system. The phase diagram comprises nine three-phase regions. The ternary compound Li₂Zn₂(MoO₄)₃ is refined by the Rietveld method. It belongs to an orthorhombic system with space group Pnma and lattice constants a = 5.1114 Å, b = 10.4906 Å, c = 17.6172 Å.     

Er-doped SiO2–Al2O3 thin films prepared by the sol–gel route

The synthesis of homogeneous and pure silica–alumina binary glasses doped with rare-earth (RE) ions such as Er³⁺ is currently a key challenge for the development of integrated optics devices such as lasers, optical amplifiers or waveguides. In this study Er³⁺-doped SiO₂–Al₂O₃ films were prepared by the sol–gel route. Aluminium sec-butoxide, Al(O-sec-C₄H₉)₃ (ASB), and tetraethoxysilane, Si(OC₂H₅)₄ (TEOS), were used as glass oxide precursors, whereas erbium was introduced as Er(NO₃)₃. The alumina content in the silica matrix was 10 at.%, while erbium doping ranged between 200 and 5000 ppm. The preparation of the starting sol–gel solution and the layer deposition by a dip-coating procedure were performed in dry-box under nitrogen atmosphere. The obtained films were subsequently annealed in air between 300 and 1000 °C. After treatment at 500 °C, layers 200 nm thick were obtained. The composition, microstructure and surface morphology of the films were investigated by X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectrometry (SIMS), glancing incidence X-ray diffraction (GIXRD) and atomic force microscopy (AFM). Crack-free, transparent, high purity films were obtained, characterised by compositional and microstructural homogeneity.     

Thermodynamic properties and phase diagrams of the binary systems B2O3–Ga2O3, B2O3–Al2O3 and B2O3–In2O3

We calculated the binary phase diagrams B₂O₃–Ga₂O₃, B₂O₃–In₂O₃ and B₂O₃–Al₂O₃, and the Gibbs energy of formation of the binary compounds, using experimental liquidus data. The B₂O₃–Ga₂O₃ system is of industrial importance, because liquid B₂O₃, in which Ga₂O₃ is not very soluble, is used to protect GaAs during growth of single crystals of GaAs. During recovery of noble metals B₂O₃ is added to slags containing Al₂O₃ to lower the melting point and the viscosity. The B₂O₃–In₂O₃ system is of much less importance to industry. In all three systems we have a liquid miscibility gap, and also solid binary compounds, none of which melt congruently. The miscibility gaps are not surprising, because even in the B₂O₃–Bi₂O₃ system where four congruently melting compounds are present, a liquid miscibility gap exists close to B₂O₃.     

冷却-加热对CaO-Al2O3-SiO2系玻璃析晶动力学的影响

以CaO-Al2O3-SiO2系玻璃为研究对象,采用Ozawa方程、Kissinger方程和JMA修正方程研究了冷却方式和加热温度对玻璃析晶动力学的影响。结果表明:化学组成相同的玻璃,冷却速度和加热温度对其析晶活化能E、Avrami指数n和析晶速率指前因子ν都有影响,但加热温度对析晶活化能E的影响更大,并在750℃出现极大值现象。通过玻璃析晶试验发现:冷却速度和加热温度对微晶玻璃主次晶相的析出没有影响,主、次晶相分别是钙长石和榍石。冷却速度和加热温度对析晶活化能E的影响主要来源于析出主、次晶相的比例不同。     

Subsolidus phase relations in the ZnO–MoO3–B2O3, ZnO–MoO3–WO3 and ZnO–WO3–B2O3 ternary systems

The subsolidus phase relations in the ZnO–MoO₃–B₂O₃, ZnO–MoO₃–WO₃ and ZnO–WO₃–B₂O₃ ternary systems have been investigated by the means of X-ray powder diffraction (XRD). There is no ternary compound in all the systems. There are five binary compounds and five tie lines in the ZnO–MoO₃–B₂O₃ system. This system can be divided into six 3-phase regions. There are three binary compounds and three tie lines in the ZnO–MoO₃–WO₃ system. This system can be divided into four 3-phase regions. There are four binary compounds and four tie lines in the ZnO–WO₃–B₂O₃ system. This system can be divided into five 3-phase regions. The possible component regions for ZnO single crystal flux growth were discussed. The phase diagram of Zn₃B₂O₆–ZnWO₄ pseudo-binary system has been constructed, and the result reveals this system is eutectic system. The eutectic temperature is 1007 °C and eutectic point component is 70 mol% Zn₃B₂O₆.     

The reduction of Eu to Eu in air and luminescence properties of Eu activated ZnO–B2O3–P2O5 glasses

A valence change from Eu³⁺ to Eu²⁺ was observed in the europium ion-doped ZnO–B₂O₃–P₂O₅ glasses prepared at high temperature in air. The fluorescence emission spectrum of the sample consists of a broad emission band ascribed to the 5d–4f transition of Eu²⁺ ion and sharp emission peaks assigned to the transitions of ⁵D_o–⁷F_J (J = 0, 1, 2, 3, and 4) of Eu³⁺ ion, indicating that part of Eu³⁺ can be reduced into Eu²⁺ in the glass. A charge compensation model is proposed. The rigid tetrahedral network structure of glasses plays an important role in stability of Eu²⁺. The fabrication conditions are also studied.     

Zr_(55)Cu_(30)Ni_5Al_(10)大块金属玻璃的等时和等温晶化(英文)

采用差示扫描量热仪(DSC)和X射线衍射仪(XRD)研究Zr55Cu30Ni5Al10大块金属玻璃的非等温晶化转变动力学和在过冷液相区的等温晶化动力学行为。在非等温过程中,采用不同方法(Kissinger,Flynn-Wall-Ozawa和Augis-Bennett)得到的Zr55Cu30Ni5Al10大块金属玻璃平均激活能彼此之间吻合很好。此外,采用Johnson-Mehl-Avrami(JMA)模型描述Zr55Cu30Ni5Al10大块金属玻璃的等温转变动力学。研究结果表明:Zr55Cu30Ni5Al10大块金属玻璃的Avrami指数n介于2.2和2.9之间,表明其晶化机制主要是扩散控制过程。在等温晶化的过程中,晶核长大主要是三维的长程有序扩散控制的过程,平均激活能为469kJ/mol。     

Subsolidus phase relationships in the system ZnO–Li2O–WO3

The subsolidus phase relationships of the system ZnO–Li₂O–WO₃ have been investigated by X-ray diffraction (XRD) analyses. There are one ternary compound, five binary compounds and eight 3-phase regions in this system. The new ternary compound Li₂Zn₂W₂O₉ was found by the powder diffraction pattern. The corresponding crystal structure of this compound was refined by Rietveld profile fitting method. It belongs to a trigonal system with space group and lattice constants are a = 5.1438(2) Å, c = 14.1052(3) Å, and its thermal property was studied.     

Phase relations in the SrO–Ga2O3–B2O3 system

The subsolidus phase relations in the SrO–Ga₂O₃–B₂O₃ system were investigated. The system contains 10 binary compounds and two ternary compounds, and can be divided into 15 three-phase regions. The new ternary compound SrGaBO₄ has two modifications (- and β-phases), both of which crystallize in the orthorhombic system but with different space groups.     

Formation of celsian from mechanically activated BaCO3–Al2O3–SiO2 mixtures

A ternary mixture BaCO₃–Al₂O₃–SiO₂ was mechanically activated for different lengths of time. Chemical composition of the mixture corresponded to BaAl₂Si₂O₈–BAS. As a function of activation time, reaction course was followed in the temperature range 750–1200°C. Reaction of celsian formation was followed using thermogravimetry as well as conventional and high-temperature X-ray diffractometry. The obtained data show that reaction rate increases with prolonged activation time, under the same conditions of thermal treatment. Formation of hexacelsian via a series of solid state reactions involving Ba-silicates, was favoured with increasing activation time. Direct formation of monoclinic celsian was retarded, however, with prolonged activation.     

An Investigation of the thermal degradation of the intumescent coating containing MoO3 and Fe2O3

An intumescent flame retardant coating was prepared using an ammonium polyphosphate (APP)-pentaerythritol (PER)-melamine (MEL) intumescent flame retardant (IFR) system. Molybdenum trioxide (MoO₃) and ferric oxide (Fe₂O₃) were used as modifiers to improve the thermal stability of the APP-PER-MEL coating. The effects of MoO₃ and Fe₂O₃ on the thermal stability of the residue chars were studied using thermogravimetric analysis (TGA), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) and scanning electric microscopy (SEM). The TGA results showed that adding MoO₃ and Fe₂O₃ increased the residue weights of the APP-PER-MEL coatings. XPS analysis demonstrated that the thermal stability of the coatings was improved. SEM images of chars illuminated that MoO₃ and Fe₂O₃ improved the outer and inner surface structure of the residue char layer. All the results indicated that MoO₃ and Fe₂O₃ were effective modifiers to improve the thermal stability of the APP-PER-MEL coating.