The crystallization behaviour of bismuth germanate glasses

Glassy samples containing Bi₂O₃ and GeO₂ in different ratios were prepared and absorption measurements were performed on the samples in the ultraviolet region in order to determine the optical behaviour. Thermal analysis performed on the vitreous samples gave the glass transition temperature and the crystallization temperature. The main crystalline phases separated during the heat treatment were Bi₄Ge₃O₁₂ (BGO) and Bi₂GeO₅. The activation energy of the crystallization process of the sample BGO (1∶3) was measured using the isothermal method, and the value obtained was 47.1 kcal mol⁻¹; the reaction order was equal to 1.1.     

Synthesis of a bismuth germanium oxide source material for Bi4Ge3O12 crystal growth

A technique has been developed for the preparation of a modified source material for the crystal growth of bismuth orthogermanate, Bi₄Ge₃O₁₂ (BGO). It includes dispersion of molten bismuth through mixing with germanium oxide (GeO₂) powder in a rotating reactor, followed by oxidation with oxygen. The source material thus prepared contains, in addition to bismuth and germanium oxides, considerable proportions of germanates (Bi₂GeO₅, Bi₄Ge₃O₁₂, and Bi₁₂GeO₂₀), which improve the reactivity of the components of the source material during homogenization before the crystal growth process. After sintering at 880°C, the density of the modified source material (3.9 g/cm³) is a factor of 1.5 higher than that of a source material prepared from Bi₂O₃ and GeO₂ powders. BGO crystals grown using the synthesized source material possess good scintillation characteristics.     

From eulytine to the ambidextrous crystal via the amorphous route: Lead & calcium bismuth germanate glasses

Lead and calcium bismuth germanate glasses containing at least 40 mole% GeO₂ were prepared. Physical properties and infrared spectra suggest that for glasses close to the PbO · Bi₂O₃ · 2GeO₂ composition: (a) packing efficiency is directly dependent upon cation size, (b) refraction is dependent upon cation type, (c) calcium can substitute for lead in nearly ideal fashion, (d) the open eulytine arrangement of a 2Bi₂O₃ · 3GeO₂ glass has collapsed, and (e) Ge₂O₇ dimers and small chains of GeO₄ tetrahedra (characteristic of Pb₅Ge₃O₁₁ and PbGeO₃ respectively) may persist. These findings offer a rationale for the limited yields of Ca₃Al₂Ge₃O₁₂ garnets obtained from such melts at high temperatures. A noncubic crystalline phase that may be Pb₃Bi₂Ge₃O₁₂ is also reported.     

Direct atomic emission analysis of bismuth and germanium oxides and bismuth orthogermanate crystals using two-jet arc plasma

Simple, high-speed procedures have been proposed for direct analysis of Bi₂O₃, GeO₂, and crystals of bismuth orthogermanate (BGO) by atomic emission spectroscopy with a high-power two-jet arc plasma as an excitation source. The detection limits for 36 impurities have been shown to lie in the ranges of 0.008–2 (Bi₂O₃), 0.006–4 (GeO₂), and 0.008–3.5 μg/g (BGO).     

Synthesis and High-Temperature Heat Capacity of Dy<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript> and Ho<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Dy₂Ge₂O₇ and Ho₂Ge₂O₇ pyrogermanates have been prepared by solid-state reactions in several sequential firing steps in the temperature range 1237–1473 K using stoichiometric mixtures of Dy₂O₃ (or Ho₂O₃) and GeO₂. The heat capacity of the synthesized germanates has been determined as a function of temperature by differential scanning calorimetry in the range 350–1000 K. The experimentally determined C _p (T) curves of the dysprosium and holmium germanates have no anomalies and are well represented by the Maier–Kelley equation. The experimental C _p (T) data have been used to evaluate the thermodynamic functions of the Dy₂Ge₂O₇ and Ho₂Ge₂O₇ pyrogermanates: enthalpy increment H°(T)–H°(350 K), entropy change S°(T)–S°(350 K), and reduced Gibbs energy Ф°(T).     

Phase relations and crystallization of glass in the system PbO-GeO2

Thermal properties and chemical compositions of glasses suitable for crystallization of ferro-electric Pb₅Ge₃O₁₁ are described. The crystallization of lead germanate glass was investigated by DTA and X-ray diffraction. In the range from 62 to 62.5 of PbO in mole per cent, Pb₅Ge₃O₁₁ was obtained as a single phase after a heat treatment. In the chemical composition around 5PbO·3GeO₂ in the binary system of PbO-GeO₂, Pb₅Ge₃O₁₁ and two new phases of Pb₃Ge₂O₇ and Pb₃GeO₅ were found to exist. The crystal structure of Pb₃Ge₂O₇ had a hexagonal symmetry witha=10.16 Å andc=19.37 Å, and Pb₃GeO₅ was classified into orthorhombic system witha=4.85 Å,b=15.52 Å and c=11.77 Å.     

Effect of quenching rate on the structure, ion transport, and crystallization kinetics in lithium-rich phosphate glass

The report investigates the effect of quenching rate on the structure, lithium ion dynamics, and crystallization kinetics of mol% 60Li₂O–40P₂O₅ glass. Quenching rate of the order of 10⁵ K s^?1 has been achieved using a twin-roller rapid quenching setup. Raman and FT-IR studies reveal that the rapidly quenched glass is more disordered with a reduced amount of pyrophosphate structural units (P₂O₇ ^4?) in the glass matrix as compared with the conventionally quenched glass. Non-isothermal differential scanning calorimetry brings out that the rapidly quenched glass undergoes three-phase crystallization while the conventionally quenched glass depicted predominantly single-phase crystallization. The phases are identified as lithium metaphosphate (LiPO₃), pyrophosphate (Li₄P₂O₇), and orthophosphate (Li₃PO₄). The activation energy for crystallization for the major phase Li₄P₂O₇ calculated using thermoanalytical methods turns out to be 287 kJ mol^?1. The above structural differences between the rapidly and conventionally quenched glasses result in superior conduction characteristics for the rapidly quenched glass depicting ionic conductivity of 1.0 × 10^?6 S cm^?1 at 343 K with an activation energy of 0.63 eV for lithium ion motion. Microstructural studies on the glass ceramics divulge surface, 2D, and 3D crystal growth mechanism for lithium meta-, pyro-, and ortho-phosphate phases, respectively.     

Relaxor behaviour and dielectric properties of BiFeO3 doped Ba(Zr0·1Ti0·9)O3 ceramics

Ba_1???x Bi _x (Ti_0·9Zr_0·1)_1???x Fe _x O₃ ( x = 0–0·075) ceramics are prepared using a conventional solid state reaction method. X-ray diffraction shows the presence of a single phase. Addition of Bi^3?+? and Fe^3?+? strongly influences the crystal structure and dielectric properties of the ceramics. The evolution from a normal ferroelectric to a relaxor ferroelectric is emphasized. Ba_0·99Bi_0·01(Ti_0·9Zr_0·1)_0·99Fe_0·01O₃ ceramic shows a relaxor behaviour at room temperature with Δ T _m =12 K. P– E hysteresis loop of the composition, x = 0·007, shows a remanent polarization ( P _r ) of 0·5 μC/cm² with a coercive field ( E _C ) of 2 kV/cm. Raman spectra of all compounds are performed and correlated well with the X-ray diffraction and dielectric measurement results.     

Synthesis and High-Temperature Heat Capacity of Sm<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript> and Eu<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Sm₂Ge₂O₇ and Eu₂Ge₂O₇ germanates have been prepared by solid-state reactions via multistep firing of stoichiometric mixtures of Sm₂O₃ (Eu₂O₃) and GeO₂ in air at temperatures from 1273 to 1473 K. The molar heat capacity of the samarium and europium germanates has been determined by differential scanning calorimetry in the range 350–1000 K and the C _p (T) data have been used to evaluate their thermodynamic properties.     

Ce-doped bismuth ferrite thin films with improved electrical and functional properties

Bi_1?xCe_xFeO₃ (BCFO) thin film capacitors (x = 0 to 0.2) are fabricated on indium tin oxide coated corning glass substrate by chemical solution deposition method. X-ray diffraction results show a partial phase transition from rhombohedral to tetragonal structure induced in BCFO thin film having preferred (110) orientation with increase in Ce dopant concentration. Current density–field (J–E) characteristics indicate that the leakage current density reduces by several orders of magnitude in Ce-doped BFO thin films resulting from smaller grain sizes and smoother surfaces. Space-charge-limited current and Fowler–Nordheim tunneling are identified as dominating leakage behavior in BCFO thin film capacitors at moderate and high field regions, respectively. Enhanced ferroelectric response with well-saturated (P–E) hysteresis loop is observed for Bi_0.88Ce_0.12FeO₃ thin film having high remnant polarization (P _r—127 µC/cm²) at an applied field of 1080 kV/cm. Bi_0.88Ce_0.12FeO₃ thin film exhibiting well-defined capacitance–field (C–E) butterfly loop with dielectric loss (tan δ—0.03) measured at 10 kHz suggested good ferroelectric properties with high tunability of about 88 %.     

Alteration of amorphous Bi4Ge3O12 by Tl2O and Na2O

Ternary thallium and sodium bismuth germanate glasses were prepared and their densities refractive indices, and infra-red spectra obtained. The effect of univalent cations on the stability of the arrangement of decoupled GeO₄ tetrahedra in amorphous Bi₄Ge₃O₁₂ was compared with the effect of divalent cations. The molar volumes of glasses with the nominal mol% composition 20 M₂O(MO).20 Bi₂O₃.60 GeO₂ are directly related to the size and charge type of M^z+. However, the molar volumes of such glasses are inversely related to the ionic potential (z/r) of M^z+. The infra-red spectra of these ternary glasses exhibitv _Ge?O shifts that reflect the presence of both isolated and small clusters of GeO₄ tetrahedra compared to amorphous Bi₄Ge₃O₁₂. This slight increase in the degree of polymerization appears to be directly related to the ionic potential of M^z+.     

Low Temperature Heat Capacity of Layered Superconductors SrNi2Ge2 and SrPd2Ge2

Low-temperature heat capacity C(T) of the weakly electron-correlated SrNi₂Ge₂ 122-layer compound undergoes a superconducting transition with onset at 1.4 K and a bulk T _c =0.75 K, where heat-capacity jump ratio ΔC(T _c )/γT _c =0.88–1.05. A small average superconducting energy gap E _g (ave)=2.21 kT _c =0.14 meV is derived for this multi-gap superconductor. Similar results for isostructural SrPd₂Ge₂ include T _c (onset)=3.5 K, bulk T _c of 2.92 K, ΔC(T _c )/γT _c =0.70 and E _g (ave)=2.54 kT _c =0.64 meV. The higher T _c onset could be associated with stoichiometric 1:2:2 grains in the polycrystalline samples. In addition, deviations of E _g /kT _c from the BCS ratio of 3.5 suggest that, just like their iron-based counterpart, these 122-layer germanides may also exhibit an unconventional, fully-opened multi-gap s-wave superconductivity.     

Dielectric and ferroelectric characteristics of [(Bi0.5Na0.5)0.94Ba0.06]1−xSrxTiO3 ceramics

Effects of Sr-substitution upon dielectric and ferroelectric characteristics of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ ceramics have been investigated together with the structure. [(Bi_0.5Na_0.5)_0.94Ba_0.06]_1?xSr_xTiO₃ solid solutions are formed in the entire composition range investigated here (x = 0–0.3), and there are two kinds of symmetries: P4bm and R3c. A morphotropic phase boundary separating P4bm and R3c is observed at x = 0.025. There are two dielectric anomalies in the permittivity versus temperature curve. Sr-substitution significantly enhances the low-temperature dielectric relaxation (around T _d ) and lowers the phase transition temperature (high-temperature dielectric anomaly at T _m ). The saturated polarization–electric field (P–E) hysteresis loops are determined further below T _d , and the pinched P–E hysteresis loops are generally indicated between T _d and T _m . With increasing Sr-content, T _d increases at first and then turns to decrease above x = 0.10, while T _m decreases continuously. Moreover, the pinched P–E hysteresis loops become very weak at x > 0.25. Sr-substitution changes the stabilization of the nonpolar state above T _d , and suppresses the electric field induced phase transition.     

Dynamics of energy absorption versus crystallization in Bi4Ge3O12 (BGO) amorphous materials

Theoretical and experimental determinations show that the intrinsic luminescence of BGO materials is strongly influenced by GeO₄⁻ tetrahedra around Bi³⁺ ions. Besides Bi³⁺ transitions, the excitonic spectra mask the BGO bandgap. Theoretical computations give the bandgap at 5.19 eV compared with the experimental one at 5.17 eV in BGO crystals and a significant decrease at 3.26 eV in the amorphous materials. This is due to the high disordering of the GeO₄⁻ tetrahedral which also reduces the refractive index of the amorphous materials. Formation of excitonic states and their overlap with the Bi³⁺ transitions suggests that the energy absorption takes place via the p-electrons of the O₂⁻ ions and is then transferred to the Bi³⁺p-electrons (excited states) close to the conduction band. Light emission appears after de-excitation to the ground state.     

Effect of some VA group modifiers on R2O3 (R = Sb,Bi)–ZnF2–GeO2 glasses doped with CuO by means of spectroscopic and dielectric investigations

Transparent glasses 40Sb₂O₃–20ZnF₂–(40 − x)GeO₂:xCuO, and 40Bi₂O₃–20ZnF₂–(40 − y)GeO₂:yCuO with x = 0, 0.6 and 0 ≤ y ≤ 1 wt% were prepared by melt quenching technique and were characterized by XRD and differential thermal analysis. Spectroscopic studies like optical absorption, FTIR, Raman, EPR and dielectric parameters (such as ?′, loss(tan δ), and σ_ac) were carried out to examine the modifier and dopant effect on zinc germanate glass network. Optical absorption and EPR data have revealed that the environment of Cu²⁺ ions is more ionic in bismuth series rather than antimony glasses. Reduced bismuth ions have been found in pure and at lower concentration of dopant in Bi₂O₃ mixed glasses, which are useful for IR amplifications. FTIR and Raman spectra have indicated the conversion of GeO₄ to GeO₆ structural units by forming cross linking bonds like Bi–O–Ge, Ge–O–Cu, etc., and open the glass network with integration of Bi₂O₃ and CuO doping. It is also confirmed by decreasing T_g and E_g values. The temperature dependence of dielectric parameters at different frequencies was interpreted in terms of structural changes in the glass network.     

Structure and electrical properties of Bi0.5Na0.5TiO3-Y0.5Na0.5TiO3-BaTiO3 lead-free piezoelectric ceramics

New (1 – x ? y)Bi_0.5Na_0.5TiO₃-xY_0.5Na_0.5TiO₃-yBaTiO₃ lead-free ceramics have been prepared by a conventional ceramic fabrication technique, and their structure and electrical properties have been studied. A morphotropic phase boundary (MPB) of rhombohedral and tetragonal phases is formed at 0.04 < y < 0.10. As compared to pure Bi_0.5Na_0.5TiO₃ ceramic, the partial substitutions of Y³⁺ for Bi³⁺ and Ba²⁺ for (Bi_0.5Na_0.5)²⁺ in the A-sites of Bi_0.5Na_0.5TiO₃ lower effectively the coercive field E _c and increase the remanent polarization P _r of the ceramics. Because of low E _c, large P _r and the MPB, the ceramics with x = 0–0.02 and y = 0.06 exhibit the optimum piezoelectric properties: d ₃₃ = 155–159 pC/N and k _p = 28.8–36.7%. The temperature dependences of dielectric properties of the ceramics show relaxor-like behaviors. The ferroelectric properties at different temperature suggest that the ceramics may contain both the polar and non-polar regions near/above T _d.     

Orientation control of a seeding layer and its effect on structure, ferro- and piezoelectric properties of sol–gel derived Bi3.15Nd0.85Ti3O12 thin films

We report on the orientation control of a seeding layer for sol–gel derived Bi_3.15Nd_0.85Ti₃O₁₂ thin films by optimizing the layer thickness and processing parameters including annealing temperature and time. A 75-nm-thick seeding layer with (100) preferential orientation can be obtained on SiO₂/Si substrate by annealing at 560 °C for 3 min. The Bi_3.15Nd_0.85Ti₃O₁₂ thin film grown on this optimized seeding layer exhibits a much higher relative intensity of (200) X-ray diffraction peak, which in turn results in more squared P–E hysteresis loops, larger remanent polarization (2P _r ~ 62 μC/cm²) and piezoelectric coefficient (d ₃₃ ~ 74 pm/V) compared to the film without the optimized first layer prepared using the conventional sequential layer annealing method.     

Bi4Ti3O12 modified low voltage ZnO-based varistors: microstructure, electrical properties and aging characteristics

The effects of Bi₄Ti₃O₁₂ addition on the microstructure, electrical properties and aging characteristics of ZnO-based varistors were investigated. The addition of Bi₄Ti₃O₁₂ can reduce the formation of Zn₂TiO₄ spinel phase and promote the growth of ZnO grain. Bi₄Ti₃O₁₂ doped ZnO-based varistors sintered at 1,130 °C possessed excellent performance of I _L = 2.9 μA, E _1mA = 29.7 V/mm, α = 30.2, and good surge absorption capability with %△E _1mA = ?3.5 % for 500 A 8/20 μs impulse current. In addition, the varistors exhibited the most stable accelerated aging characteristics with %△E _1mA = ?0.3 % for DC accelerated aging stress of 125 °C/7 h. These results revealed that Bi₄Ti₃O₁₂ addition is highly beneficial to attain enhanced varistor properties of ZnO ceramics.     

Growth of Sillenite-Structure Single Crystals

The main processes for preparing bulk single crystals and films of photorefractive and piezoelectric Bi₁₂M _x O_20±δ (M = Group II–VIII elements) sillenite compounds are considered. Experimental data are summarized on the crystal growth of Bi₁₂M _x O_20±δ from the melt and under hydrothermal conditions, and the key morphological features of sillenites are analyzed. Various types of macroscopic growth defects in sillenite-type crystals are described, and their origin is discussed. The compositions of second-phase inclusions in undoped and doped (Group I–VIII elements) Bi₁₂SiO₂₀, Bi₁₂GeO₂₀, and Bi₁₂TiO₂₀ single crystals are presented, and the main physicochemical properties of various Bi₁₂M _x O_20±δ crystals are summarized.     

Synthesis, IR, crystallization and dielectric study of (Pb, Sr)TiO 3 borosilicate glass–ceramics

Eleven glass compositions were prepared by melt and quench method with progressive substitution of SrO for PbO (0?≤?x?≤ 1·0) with a step-wise increment of 0·10 in the glass [(Pb _x Sr_1???x )OTiO₂]–[(2SiO₂B₂O₃)]–[BaO·K₂O]·Nb₂O₅ (mol percentage) system. The infrared spectra (IR) of various glass compositions in the above mentioned glass system was recorded over a continuous spectral range 400–4000 cm^???1 to study their different oxides structure systematically. Differential thermal analysis (DTA) was recorded from room temperature (~27 °C) to 1400 °C employing a heating rate of 10 °C /min to determine glass transition temperature, T _g and crystallization temperature, T _c. The melting temperature, T _m, of these glass compositions was found to be in the range 597–1060 °C depending on the composition under normal atmospheric conditions. T _g and T _m of glasses were found to increase with increasing SrO content. X-ray diffraction analysis of these glass–ceramic samples shows that major crystalline phase of the glass–ceramic sample with x ≤ 0·5 was found to have cubic structure similar to SrTiO₃ ceramic. Scanning electron microscopy has been carried out to see the surface morphology of the crystallites dispersed in the glassy matrix.