Magnetite nanoparticles prepared by the crystallization of Na2O–Fe2O3–B2O3–SiO2 glasses

A glass with the composition of 35Na₂O–24Fe₂O₃–20B₂O₃–20SiO₂–1ZnO (mol%) was melted, quenched, using a twin roller technique, and subsequently heat treated in the range 485–750 °C for 1–2 h. This led to the crystallization of magnetite as the sole or the major crystalline phase.Heat treatment at lower temperatures resulted in the crystallization of magnetite crystals 7–20 nm in diameter, whereas heat treatment at higher temperatures produced higher quantities of magnetite and much larger crystals. The room temperature magnetization and coercive force values were in the range of 6–57 emu g^? 1 and 0–120 Oe, respectively for the heat treated glasses.     

Second-order optical non-linearity initiated in Li2O–Nb2O5–SiO2 and Li2O–ZnO–Nb2O5–SiO2 glasses by formation of polar and centrosymmetric nanostructures

Amorphous nanoheterogeneities of the size less than 100 Å have been formed in glasses of the Li₂O–Nb₂O₅–SiO₂ (LNS) and Li₂O–ZnO–Nb₂O₅–SiO₂ (LZNS) systems at the initial stage of phase separation and examined by transmission electron microscopy, small-angle X-ray and neutron scattering. Both LNS and LZNS nanoheterogeneous glasses exhibit second harmonic generation (SHG) even when they are characterized by fully amorphous X-ray diffraction (XRD) patterns. Chemical differentiation and ordering of glass structure during heat treatments at appropriate temperatures higher T_g lead to drastic increase of SHG efficiency of LNS glasses contrary to LZNS ones in the frame of amorphous state of samples. Following heat treatments of nanostructured glasses result in crystallization of ferroelectric LiNbO₃ and non-polar LiZnNbO₄ in the LNS and LZNS glasses, respectively. Taking into account similar polarizability of atoms in LNS and LZNS glasses, the origin of the principal difference in the second-order optical non-linearity of amorphous LNS and LZNS samples is proposed to connect predominantly with the internal structure of formed nanoheterogeneities and with their polarity. Most probably, amorphous nanoheterogeneities in glasses may be characterized with crystal-like structure of polar (LiNbO₃) phase initiating remarkable SHG efficiency or non-polar (LiZnNbO₄) phase, which do not initiate SHG activity. It gives an opportunity to vary SHG efficiency of glasses in a wide rage without remarkable change of their transparency by chemical differentiation process at the initial stage of phase separation when growth of nanoheterogeneities is ‘frozen’. At higher temperatures, LiNbO₃ crystals identified by XRD precipitate in LNS glasses initiating even more increase of SHG efficiency but visually observable transparency is impaired.     

Raman and NMR study of bioactive Na2O–MgO–CaO–P2O5–SiO2 glasses

The results of a structural study combining NMR and Raman spectroscopy of several melt-derived glasses in the system Na₂O–MgO–CaO–P₂O₅–SiO₂ are presented. The Raman spectra show clear changes in the Si–O–Si vibrational modes (related to the bridging oxygen atoms, BO) and also verify the presence of non-bridging oxygen atoms (NBO), also named terminal oxygens. The intensity of the Si–O–NBO stretching mode depends on the cation concentration. It can be concluded from the NMR studies that the MgO-containing samples have orthophosphate units charge-compensated by Ca²⁺ and Mg²⁺. The silicate matrix also contains both types of two-valent cations and consists of Q² and Q¹ units. Similarly, the Na₂O-containing samples contain isolated orthophosphate units in a silicate matrix (Q² and Q³ units), both charge-compensated by mixed cations Ca²⁺ and Na⁺. These experimental data were compared with theoretical parameters given by the Stevels model, which is a suitable tool for understanding bioactive behavior of these glasses. Furthermore, results of the in vitro tests carried out in simulated body fluids are presented and compared with both Raman and NMR structural data.     

Studies of ternary Li2SO4–Li2O–P2O5 glasses

Glasses in a wide range of compositions in the ternary system xLi₂SO₄–yLi₂O–zP₂O₅ where x ranges from 0 to 30 mol%, y ranges from 35 to 55 mol% and z ranges from 25 to 50 mol% have been prepared and their properties measured using infra-red, Raman, and ³¹P magic angle spinning nuclear magnetic resonance spectroscopic techniques. We conclude that a random close packing of phosphate and sulphate ions which also leads to formation of connected voids in the structure is consistent with our data. There is also evidence for formation of condensed sulphate–phosphate species in the liquid which may be retained in the glass structure.     

Mixed alkali effect in physical and optical properties of Li2O–Na2O–WO3–B2O3 glasses

Glasses with composition xLi₂O-(30 ? x)Na₂O–10WO₃–60B₂O₃ (where x = 0, 5, 10, 15, 20, 25 and 30 mol%) have been prepared using the melt quenching technique. In the present work, the mixed alkali effect (MAE) has been investigated in the above glass system through density and modulated DSC studies. The density and glass transition temperature of the present gasses varies non-linearly, the exhibiting the mixed alkali effect. From the optical absorption studies, the values of direct optical band gap, indirect optical band gap energy (E_o) and Urbach energy(ΔE) have been evaluated. The values of E_o and ΔE vary non-linearly with composition parameter, showing the mixed alkali effect. The electronic polarizability of oxide ions, optical basicity and the Yamashita–Kurosawa's interaction parameter have been examined to check the correlation among them and bond character. Based on good correlation among electronic polarizability of oxide ions, optical basicity and the Yamashita–Kurosawa's interaction parameter, the present Li₂O–Na₂O–WO₃–B₂O₃ glasses were classified as normal ionic (basic) oxides.     

Structure and properties of NaPO3–ZnO–Nb2O5–Al2O3 glasses

In an effort to design low-melting, durable, transparent glasses, two series of glasses have been prepared in the NaPO₃–ZnO–Nb₂O₅–Al₂O₃ system with ZnO/Nb₂O₅ ratio of 2 and 1. The addition of ZnO and Nb₂O₅ to the sodium aluminophosphate matrix yields a linear increase of properties such as glass transition temperature, density, refractive index and elastic moduli. The chemical durability is also significantly, but nonlinearly, improved. The glass with the highest niobium concentration, 55NaPO₃–20ZnO–20Nb₂O₅–5Al₂O₃ was found to have a dissolution rate of 4.5 × 10^? 8 g cm^? 2 min^? 1, comparable to window glass. Structural models of the glasses were developed using Raman spectroscopy and nuclear magnetic resonance spectroscopy, and the models were correlated with the compositional dependence of the properties.     

Formation of Co2+-doped nanocrystals in La2O3–MgO–Al2O3–SiO2 glass-ceramics

Transparent glass-ceramics were synthesized by heat-treatment of glass with a composition of 5La₂O₃–13.2MgO–28.8Al₂O₃–46SiO₂–4.5TiO₂–2.5ZrO₂–0.15CoO (LMAS) (wt.%). The activation energy of crystallization and the Avrami parameter for the LMAS glass were determined from the DTA curves at different heating rates. The most two intense bands of Raman spectrum of initial glass at ~ 810 cm^?1 and ~ 900 cm^?1 were connected with the presence of [SiO₄] and [TiO₄] tetrahedral, respectively. After heat-treated at 700 °C/10 h+820 °C/8 h, the intensity of the band for [TiO₄] tetrahedral weakened, while an intensive band at ~ 800 cm^?1 for the Ti–O bond appeared. Other bands were characteristics of high-silicate network and x(MgTi₂O₅)·y(Al₂TiO₅) polycrystals. The changes reflected phase separation after heat-treatment of the initial glass. The strong absorption band of glass-ceramics centered at 580 nm can be assigned to ⁴A₂(⁴F)→⁴T₁(⁴P) and the broad absorption band at 1100–1700 nm to ⁴A₂(⁴F)→⁴T₁(⁴F) transitions of tetrahedral coordinated Co²⁺ ion. Two broad emission bands, one was around 660 nm, the other was from 800 nm to 1050 nm, of glass-ceramics correspond to the ⁴T₁(⁴P)→⁴A₂(⁴F) and ⁴T₁(⁴P)→⁴T₂(⁴F) transitions of tetrahedral coordinated Co²⁺ ions. The absorption and emission features clearly demonstrated that Co²⁺ ions were incorporated into nanocrystals and located in tetrahedral sites.     

Spectroscopic properties of Co2+ ions in La2O3–MgO–Al2O3–SiO2 glass-ceramics

Co²⁺-doped La₂O₃–MgO–Al₂O₃–SiO₂ (LMAS) glass-ceramics was synthesized by conventional method. The microstructure of LMAS GCs heat-treated at 760 °C/12 h + 930 °C/4 h was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The spectroscopic properties of Co²⁺-doped LMAS GCs were studied by absorption spectrum, excitation spectrum, and temperature dependent luminescence spectra. XRD results revealed the sizes of MgAl₂O₄ crystalline phases are about 9.1 ± 1.5 nm. The three peaks in the visible absorption band of LMAS GCs at 549 nm, 585 nm and 626 nm are connected with the transitions from ⁴A₂ level to ²A₁/²T₂(²G), ⁴T₁(⁴P) and ²E/²T₁(²G) levels, respectively, and excitations into them emit the radiation at around 666 nm. The luminescence intensity increased with temperature increasing from 10 K to 150 K, while it weakened with temperature increasing from 150 K to 350 K. These features were explained by the effects of two competing mechanisms.     

Bi precipitates in Na2O–B2O3 glasses

Bi particles of different sizes were produced in Na₂O–B₂O₃ glasses by melt quenching and heat treatment technique. Melting temperature of Bi particles was measured by differential scanning calorimetry and X-ray diffraction. Measured melting temperatures of Bi particles are lower than bulk Bi melting temperature. Results of transmission electron microscopy were analyzed for the dependence of melting temperature on particle radius. The pressure and surface energy effect on melting temperature is estimated. The melting behavior of Bi particles in Na₂O–B₂O₃ glasses depends on the difference in the interfacial energies between the solid particle/glass and liquid particle/glass, and liquid particle/glass, σ_sm−σ_lm, which is estimated to be 255×10⁻³ J m⁻².     

Performance investigation of Li2O–Al2O3–4SiO2 based glass–ceramics with B2O3, Na3AlF6 and Na2O fluxes

Influence of single fluxes (10 wt.% B₂O₃), bi-component fluxes (4 wt.% B₂O₃ + 6 wt.% Na₃AlF₆), and complex fluxes (4 wt.% B₂O₃ + 4 wt.% Na₃AlF₆ + 2 wt.% Na₂O) on the thermal kinetic parameters, microstructure, flexural strength and coefficient of thermal expansion (CTE) of Li₂O–Al₂O₃–4SiO₂ (LAS) glass–ceramics was investigated through differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscope (SEM). The results showed that complex fluxes could efficiently decrease transition temperature (T_g) and crystallization temperature (T_p), and accelerate the formation of needle-like β-spodumene crystals which benefit high flexural strength. The homogeneous LAS glass–ceramic (sample C₃) which has a high strength of 132.4 MPa and low CTE (100–650 °C) of 2.74 × 10^? 6/°C is obtained by doping of the initial LAS glass by complex fluxes of 4 wt.% B₂O₃, 4 wt.% Na₃AlF₆, and 2 wt.% Na₂O, nucleating at 630 °C/120 min and then crystallized at 780 °C/120 min. It is worthy of further investigation as a bonder of diamond composite material due to its outstanding prosperities.     

Thermal and electric transport properties of (60−x)V2O5–xAs2O3–20Fe2O3–10CaO–10Li2O unconventional glassy system

This paper presents the results of kinematical studies of glass transition and crystallization in the unconventional glassy system (60?x)V₂O₅–xAs₂O₃–20Fe₂O₃–10CaO–10Li₂O (x = 0, 10, 20, 30, 40 mol%) using differential scanning calorimetry (DSC). The glass transition temperatures (T_g), the onset crystallization temperatures (T_c), and the peak temperatures of crystallization (T_p) were found to be dependent on the compositions and the heating rates. From the dependence on heating rates of (T_g) and (T_p) the activation energy for glass transition (E_g) and the activation energy for crystallization (E_c) are calculated. The thermal stability of (60?x)V₂O₅–xAs₂O₃–20Fe₂O₃–10CaO–10Li₂O was evaluated in term of, criteria ΔT = T_c ? T_g. All the results confirm that the thermal stability increase with increasing As₂O₃ contents. From the electric–dielectric measurements it was found that, σ_dc, σ_ac(ω) and θ_D/2 decrease with increasing As₂O₃ contents. It is also observed that the dielectric constant (ε₁(ω)) and the loss factor (tan δ) decrease with increasing As₂O₃ contents in this glass system.     

Crystallization behavior during cooling and glass-forming ability of Al2O3-poor Li2O–Al2O3–SiO2 melts

The influence of K₂O/(MgO + K₂O) on some melt properties, including crystallization during cooling of melts and glass-forming ability, was investigated in the Li₂O–Al₂O₃–SiO₂ system with low Al₂O₃ content. The dependence of viscosity on K₂O/(MgO + K₂O) above 1000 °C showed a monotonic decrease due to the reduction of [MgO₄] concentration and the conductivity also decreased due to the larger ion radius of K. The temperature dependence of conductivity for all melts showed an abrupt change at one temperature due to crystallization in which temperature of crystallization decreases with increase of K₂O. The crystallization behavior near liquidus temperature was studied quantitatively by calculating the crystal volume fraction from apparent viscosity value. The glass-forming ability of the melts was discussed by using data related with viscosity and crystallization. Finally, it was suggested that the melts with K₂O/(MgO + K₂O) ? 0.75 have a good glass-forming ability.     

Structural role and coordination environment of Fe in Fe2O3–PbO–SiO2–Na2O composite glasses

The structural role, coordination geometry and valence of Fe in a series of Fe₂O₃–PbO–SiO₂–Na₂O glasses are studied by means of Fe-K-NEXAFS and EXAFS spectroscopies. Parameters for the study are the concentration of the Fe and Pb-oxides, the SiO₂/Na₂O ratio and the cast temperature. The EXAFS and NEXAFS results reveal that the role of Fe³⁺ depends on the concentration of Fe₂O₃. More specifically, in most of the studied quaternary systems, the Fe³⁺ ion is a glass former, i.e. the Fe atoms belong to FeO₄ tetrahedra that participate in the formation of the glassy network. The role of Fe as an intermediate oxide is identified only in one sample with 20 wt% Fe₂O₃, where ～80 at.% of the Fe atoms are tetrahedrally coordinated with O atoms, while the remaining ～20 at.% of the Fe atoms occupy octahedral sites. It is also revealed that the tetrahedral coordination of Fe in the vitreous matrix is destroyed when a number of parameters is altered, such as the T_cast, the (Fe + Si)/O and the SiO₂/Na₂O ratio.     

Spectral investigations on VO2+ ion doped in CaO–SrO–Na2O–B2O3 glass systems

Glasses of the (20 ? x)CaO–xSrO–(20 ? y)Na₂O–60B₂O₃ ? y (CSNB) system with (5 ≤ x ≤ 15) mol% and y = 0.1 mol% of V₂O₅ were characterized by X-ray diffraction (XRD), EPR (Electron Paramagnetic Resonance), Optical absorption Spectra and FT-IR (Fourier transform Infrared Spectroscopy) studies. EPR spectra of all the glass samples exhibit resonance signals characterstic of VO²⁺ ions. The values of spin-Hamiltonian parameters indicate that the VO²⁺ ions in CSNB glasses were present in octahedral sites with tetragonal compression and belong to C_4v symmetry. Spin-Hamiltonian parameters ‘g’ and ‘A’ were evaluated. The Optical band energy (E_opt) and Urbach energy (ΔE) were calculated from their ultra violet edges. By correlating EPR and Optical data the molecular orbital coefficients have been evaluated. IR spectra of these glasses were analyzed in order to identify the contribution of each component to the local structure that determines the physical properties of these glasses.     

Effect of alumina on the structure and properties of Li2O–B2O3–P2O5 glasses

The structure of glasses within the system Li₂O–Al₂O₃–B₂O₃–P₂O₅ has been studied through ³¹P, ¹¹B and ²⁷Al Nuclear Magnetic Resonance, and the effect of Al₂O₃ substitution by B₂O₃ and P₂O₅ network formers on the structure and properties investigated for a constant Li₂O content. Multinuclear NMR results reveal that substitution of Al₂O₃ for B₂O₃ and P₂O₅ network formers in a glass with composition 50Li₂O·15B₂O₃·35P₂O₅ produces a change in boron environment from four-fold to three-fold coordination. Meanwhile aluminum can be present in four-, five- and six-fold coordinations a higher amount of Al(IV) groups is found for increasing alumina contents. The behavior of the glass transition temperature and electrical conductivity of the glasses has been interpreted as a function of the structural changes induced in the glass network when alumina is substituted for B₂O₃, P₂O₅ or both. Small additions of alumina produce a drastic increase in glass transition temperature, while it does not change for [Al₂O₃] greater than 3 mol.%. However, the electrical conductivity shows very different behavior depending on the type of substitution; it can remain constant when B₂O₃ content decreases or sharply decrease when P₂O₅ is substituted by Al₂O₃, which is attributed to a higher amount of BO₃ and phase separation.     

BaO–B2O3–SiO2–Al2O3 sealing glass for intermediate temperature solid oxide fuel cell

Glasses in the formulation close to BaSiO₃–BaB₂O₄ eutectic compound are developed for sealing of intermediate-temperature (500–650 °C) solid oxide fuel cell (IT-SOFC). Thermal and microstructural analyses of the glasses with 0–10 mol% Al₂O₃ are also conducted. Detailed crystallization kinetics and interfacial stability of the glass in contact with yttria-stabilized zirconia (YSZ) and samaria-doped ceria (SDC) are investigated and compared. The results show that the formulation, 47BaO–21B₂O₃–27SiO₂–5Al₂O₃ (G1A5), performs the best on glass forming ability (GFA) among all tested formulations, and shows matched thermal expansion and working temperature to CeO₂-based electrolytes of IT-SOFC. Two major crystalline phases that precipitate from G1A5 above 750 °C are platy hexacelsian and BaSiO₃ grains.     

The effect of TiO2 on phase separation and crystallization of glass-ceramics in CaO–MgO–Al2O3–SiO2–Na2O system

The experiments were carried out on studying the effect of phase separation on nucleation and crystallization in the glass based on the system of CaO–MgO–Al₂O₃–SiO₂–Na₂O. In the experiments, TiO₂ was chosen as nucleating agent. Three batches of 5, 8 and 10 wt% TiO₂ substitution were investigated by the techniques of DSC, XRD, FTIR and FESEM equipped with EDS. XRD and FTIR analysis indicated that the super cooled glasses were all amorphous, the heat treatment leading to nucleation would cause a disruption of silica network which followed phase separation. The phase separation followed the generation of crystal seeds Mg(Ti, Al)₂O₆. FESEM observation and EDS analysis revealed that the more TiO₂ content of glass, the more droplet separated phase and crystal seeds after nucleation heat treatment. The main crystal phase is clinopyroxene, Ca(Ti, Mg, Al)(Al, Si)O₆, of crystallized glass.     

Role of Te valence on phases crystallized in K2O–Nb2O5–TeO2 glasses

Differences in crystalline phases between glass-ceramics and sintered ceramics in the K₂O–Nb₂O₅–TeO₂ system have been examined, particularly to obtain information on the role of Te valence on crystallization behaviors of TeO₂-based glasses. In glasses or glass-ceramics, the valence of Te⁴⁺ is retained even during heat-treatment up to around 600°C, leading to the formation of crystalline phases containing Te⁴⁺, e.g., the face-centered cubic crystalline phase. In a powder sintering method, Te⁴⁺ is easily oxidized to Te⁶⁺ during sintering at around 600°C in air and compounds such as KNbTeO₆ in which Te⁶⁺ is present are formed.     

Effect of TiO2 addition on the chemical durability of Bi2O3–SiO2–ZnO–B2O3 glass system

The effect of the substitution of ZnO for TiO₂ on the chemical durability of Bi₂O₃–SiO₂–ZnO–B₂O₃ glass coatings in hot acidic medium (0.1 N H₂SO₄ at 80 °C) for different times was studied. The thick films produced by a screen-printing method and heat treated at 700 °C/5 min were analyzed by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy. The glass from the Bi₂O₃–SiO₂–ZnO–B₂O₃ system developed Zn₂SiO₄ and a glassy phase that were readily attacked by hot 0.1 N sulfuric acid, whereas the heat treated coating from the Bi₂O₃–SiO₂–TiO₂–ZnO–B₂O₃ system presented a finer microstructure with thin interconnected Bi₄Ti₃O₁₂ crystals and a glassy phase more resistant to hot 0.1 N sulfuric acid attack etching.     

Composition analysis of glasses in the PbBr2–PbCl2–PbF2–PbO–P2O5 system

Composition change during the melting process of some glasses in the PbBr₂–PbCl₂–PbF₂–PbO–P₂O₅ system melted at 450–470°C for 15 min was studied. Results show that there was a remarkable difference between the batch composition and the analyzed composition. Large amount of P, Br, Pb, and Cl were lost mainly in the form of PbBr₂, PbCl₂ and P₂O₅. The content of O is influenced by two factors. The incomplete decomposition of NH₄H₂PO₄ or the reaction between P₂O₅ and H₂O in the atmosphere increases the content of O, while the volatilization of P₂O₅ decreases the content of O.