Properties and structure of RO---Na2O---Al2O3---P2O5 (R = Mg, Ca, Sr, Ba) glasses

The properties and structure of (45 - x)RO · xNa₂O · 2.5Al₂O₃ · 52.5P₂O₅ (R = Mg, Ca, Sr, Ba, 0 x 31 mol%) glasses were investigated. The variation in the molar volumes of glasses in the MgO series is closely related to the formation of the end groups in the glasses with the substitution of Na⁺ ions for Mg²⁺ ions, resulting in a variation of the density and refractive index of the glasses. The properties of glasses containing CaO in terms of Na₂O substitution depend mainly on the low field strength of Na⁺ ions substituting for CaO even though the end groups occurring in the glasses increased. The variation in properties of the glasses containing SrO and BaO, some of which were substituted by Na₂O, could be explained by differences in masses, field strength and polarizability between the Na⁺ ions and the alkaline-earth ions due to a small variation in the structure of the glasses despite Na₂O substitution.     

Effects of CaO on crystallization properties in BaO-SrO-TiO2-SiO2 glass-ceramics

The role of calcium oxide (CaO) was investigated in the crystallization of BaO-SrO-TiO₂-SiO₂ glass. The CaO dopant altered the oriented growth facets of crystal unit cells in the glass-ceramics. The crystallites are acicular in micron scale in the samples having as small as 1% CaO dopant, but are long granular in the nanometer scale in the sample without CaO. The glass-ceramics which have nano crystallites are observed with a less crystallization density qualitatively, a higher transmissivity in the wavelength range of 200-2600 nm, and 30% lower piezoelectric coefficient, d₃₃, at 9.5 ± 0.3 pC/N than those glass-ceramics having CaO in the study.     

Electric conductivity of glasses in the system Na2O/CaO/SiO2/Fe2O3

The addition of polyvalent transition metal ions to the usually insulating traditional soda-lime-silica glasses can lead to semiconducting properties. We report on synthesis of glasses and glass-ceramics in a soda-lime-silicate based system containing Fe₂O₃ in the concentration range from 5 to 30 mol%. Two sub-systems were considered, in one of them the ratio [Na₂O]/[Fe₂O₃] was varied while in the other one, the ratio [SiO₂]/[Fe₂O₃] was changed. The phase composition of the synthesized products was characterized by X-ray diffraction and energy dispersive X-ray analysis, while the electrical properties were studied by impedance spectroscopy. Partially crystallized non-reduced samples are semiconducting even at room temperature while the glassy samples (both reduced and non-reduced) exhibit semiconducting properties at temperatures equal or larger than 100 °C. An attempt is done to predict the physical approximation explaining the conduction process in the glasses.     

Crystallization processes of Li2O-Ga2O3-SiO2-NiO system glasses

Crystallization processes of Li₂O-Ga₂O₃-SiO₂-NiO system glasses have been studied by X-ray diffraction, differential calorimetry and optical absorption. Transparent glass-ceramic containing LiGa₅O₈:Ni²⁺ as the sole crystalline phase has been obtained from glass with the composition of 13Li₂O-23Ga₂O₃-64SiO₂-0.1NiO (in mol%) by the heat treatment in the temperature range from 923 to 953 K. It was revealed that the specific surface area of samples enhances crystallization of LiGaSi₂O₆ but obstructed that of LiGa₅O₈. LiGa₅O₈ grew to nano-sized crystallites dispersed in the glass matrices and did not affect the transparency seriously. In contrast, LiGaSi₂O₆ grew to crystallites with diameters more than 100 nm on the surface and made the glasses opaque. Optical absorption measurements revealed that doped Ni²⁺ occupied five-folded trigonal bipyramidal sites in the as-quenched glass matrices but six-folded octahedral sites of precipitated LiGa₅O₈ in the glass-ceramics. It was confirmed that transparent glass-ceramic containing Ni²⁺:LiGa₅O₈ was effectively obtained by the heat treatment at a temperature of 953 K for 10 h.     

Phase separation and crystallization in the system SiO2-Al2O3-P2O5-B2O3-Na2O glasses

The phase separation and crystallization behavior in the system (80 − X)SiO₂ · X(Al₂O₃ + P₂O₅) · 5B₂O₃ · 15Na₂O (mol%) glasses was investigated. Glasses with X = 20 and 30 phase separated into two phases, one of which is rich in Al₂O₃-P₂O₅-SiO₂ and forms a continuous phase. Glasses containing a larger amount of Al₂O₃-P₂O₅ (X = 40 and 50) readily crystallize and precipitates tridymite type AlPO₄ crystals. It is estimated that the phase separation occurs forming continuous Al₂O₃-P₂O₅-SiO₂ phase at first, and then tridymite type AlPO₄ crystals precipitate and grow in this phase. Highly transparent glass-ceramics comparable to glass can be successfully obtained by controlling heat treatment precisely. The crystal size and percent crystallinity of these transparent glass-ceramics are 20-30 nm and about 50%, respectively.     

Dependence of fluorescence properties on substitution of BaF2 for BaO in barium gallo-germanate glass

3.5 mol%, 6.5 mol%, 9.5 mol%, and 12.5 mol% BaF₂ were gradually substituted for BaO in 0.3 mol% Tm₂O₃ doped 12.5 BaO-12.5 Ga₂O₃-75 GeO₂ (BGG) glasses to study the effect of the substitution on the OH⁻ elimination and emission properties. The FTIR spectral demonstrated that the substitution effectively eliminated OH⁻ groups and 9.5 mol% BaF₂ was enough for the OH⁻ elimination. The J-O parameters of all the samples were calculated according to J-O theory. The calculation showed that the Ω₂ parameter decreased monotonically with BaF₂ content increasing, while Ω₄ and Ω₆ did not change much. The radiative lifetime increased while BaF₂ content increased as well. The emission cross section of ³F₄ → ³H₆ transition was calculated by the F-L formula. However, it decreased with the gradual BaF₂ addition.

Research Highlights

? OH⁻ groups were eliminated by the substitution of BaF₂ for BaO in (BGG) glass. ? The optimal substitution level of BaF₂ was 9.5 mol% for OH⁻ elimination. ? The Ω₂ parameter decreased monotonically by the elimination. ? The emission cross section of ³F₄ → ³H₆ transition was decreased by the substitution.     

Effect of BaO content on the sintering and physical properties of BaO-B2O3-SiO2 glasses

A BaO-B₂O₃-SiO₂ glass system was chosen as a candidate composition for the application to Pb-free low temperature sinterable glass. The effect of BaO content on the crystallization, sintering behavior, and properties of the glasses was examined. Both the glass transition temperature and crystallization temperature decreased as the BaO content increased. Crystallization easily occurred during sintering with a BaO content of more than 50 mol%, which effectively inhibited the over-firing phenomenon. The dielectric characteristics and thermal expansion coefficient of the glasses were examined and the results were explained on the basis of the crystallization and densification of the specimens.     

Thermal, chemical, optical properties and structure of Er-doped and Er/Yb-codoped P2O5-Al2O3-ZnO glasses

This study was explored in series of the optical, thermal, and structure properties based on 60P₂O₅-10Al₂O₃-30ZnO (PAZ) glasses system that doped with varied rare-earth (RE) elements Yb₂O₃/Er₂O₃. The glass transition temperature, softening temperature and chemical durability were increased with RE-doping concentrations increasing, whereas thermal expansion coefficient was decreased. In the optical properties, the absorption and emission intensities also increase with RE-doping concentrations increasing, When Er₂O₃ and Yb₂O₃ concentrations are over than 3 mol% in the Er³⁺-doped PAZ system and Yb³⁺-doped concentration is over than 3 mol% for Er³⁺/Yb³⁺-codoped PAZ system, the emission intensity significantly decreases presumably due to concentration quenching, formation of the ions clustering, and OH⁻ groups in the glasses network. It is suggested that the maximum emission cross-section (σ_e) is 7.64 × 10^− 21 cm² at 1535 nm is observed for 3 mol% Er³⁺-doped PAZ glasses. Moreover, the maximum σ_e × full-width-at-half-maximum is 327.8 for 5 mol% Er³⁺-doped PAZ glasses.     

Compositional dependence of ultraviolet fluorescence intensity of Ce in silicate, borate, and phosphate glasses

Fluorescence spectra of Ce³⁺ ions in silicate, borate, and phosphate glasses melted in Ar were measured. The relative fluorescence intensity of Ce³⁺ in the ultraviolet region increased in the order of R = Ba, Ca, Sr, and Mg in the 20Li₂O-20RO-60SiO₂ glass samples and with decreasing BaO content in the BaO-B₂O₃ glass samples, respectively. In contrast, the relative fluorescence intensity of Ce³⁺ did not change with varying the glass composition in phosphate glass samples. The compositional dependence of the relative fluorescence intensity of Ce³⁺ is discussed in terms of redox reaction of Ce³⁺-Ce⁴⁺ in oxide glasses.     

Effects of Nb2O5 Replacement by Er2O3 on elastic and structural properties of 75TeO2-(10 − x)Nb2O5-15ZnO-(x)Er2O3 glass

Tellurite 75TeO₂-(10 − x)Nb₂O₅-15ZnO-(x)Er₂O₃; (x = 0.0-2.5 mol%) glass system with concurrent reduction of Nb₂O₅ and Er₂O₃ addition have been prepared by melt-quenching method. Elastic properties together with structural properties of the glasses were investigated by measuring both longitudinal and shear velocities using the pulse-echo-overlap technique at 5 MHz and Fourier Transform Infrared (FTIR) spectroscopy, respectively. Shear velocity, shear modulus, Young's modulus and Debye temperature were observed to initially decrease at x = 0.5 mol% but remained constant between x = 1.0 mol% to x = 2.0 mol%, before increasing back with Er₂O₃ addition at x = 2.5 mol%. The initial drop in shear velocity and related elastic moduli observed at x = 0.5 mol% were suggested to be due to weakening of glass network rigidity as a result of increase in non-bridging oxygen (NBO) ions as a consequence of Nb₂O₅ reduction. The near constant values of shear velocity, elastic moduli, Debye temperature, hardness and Poisson's ratio between x = 0.5 mol% to x = 2.0 mol% were suggested to be due to competition between bridging oxygen (BO) and NBO ions in the glass network as Er₂O₃ gradually compensated for Nb₂O₅. Further addition of Er₂O₃ (x > 2.0 mol%) seems to further reduce NBO leading to improved rigidity of the glass network causing a large increase of ultrasonic velocity (v_L and v_S) and related elastic moduli at x = 2.5 mol%. FTIR analysis on NbO₆ octahedral, TeO₄ trigonal bipyramid (tbp) and TeO₃ trigonal pyramid (tp) absorption peaks confirmed the initial formation of NBO ions at x = 0.5 mol% followed by NBO/BO competition at x = 0.5-2.0 mol%. Appearance of ZnO₄ tetrahedra and increase in intensity of TeO₄ tbp absorption peaks at x = 2.0 mol% and x = 2.5 mol% indicate increase in formation of BO.     

Effect of P2O5 on the early stage crystallization of K-fluorrichterite glass-ceramics

The addition of 2 mol% P₂O₅ to stoichiometric K-fluorrichterite (KNaCaMg₅Si₈O₂₂F₂, KFR) has been reported to enhance the mechanical properties and improve the in vitro biocompatibility of this glass-ceramic by promoting the formation of enstatite and fluorapatite (FA). Here, the effect of further increasing the P₂O₅ concentration on phase evolution of KFR has been investigated. XRD data showed that mica crystallized in samples with 4 and 5 mol% P₂O₅ (GP4 and GP5, respectively) at 650 °C, but no diopside was detected at higher temperatures, in contrast with the general phase evolution in KFR based glass-ceramics. More importantly, however, the addition of ?4 mol% P₂O₅ induced phase separation of the glass into a silica glass matrix and phosphate rich droplets prior to crystallization. EDS traces taken from samples heat-treated at 600 °C, revealed that the silica glass matrix was deficient in Mg and unlikely to be the host for crystallization of mica. Conversely, the P₂O₅ rich regions contained excess Mg and were considered to be the host for the formation of mica and FA.     

Sol–gel synthesis and characterization of unexpected rod-like crystal fibers based on SiO2–(1-x)CaO–xSrO–P2O5 dried-gel

Sol–gel technique has several benefits for the preparation of glass, and morphology can be better controlled compared to conventional methods. In this research, new sol–gel derived bioactive glasses based on SiO₂–CaO–SrO–P₂O₅ dried-gel were synthesized and characterized. Herein, a series of 58S bioactive glasses with the composition of 60%SiO₂–36%(CaO/SrO)–4%P₂O₅ (mol%) were synthesized, and the effect of adding strontium (Sr) to the glass structure SiO₂–(1-x)CaO–xSrO–P₂O₅ (where x = 0, 0.5, 0.1, 0.25, 0.5 and 1) was investigated by gradually substitution of Sr with calcium (Ca). The obtained results indicated that the Sr free sample totally takes amorphous state indicative of the internal disorder, glassy nature and non-crystalline states of this material. Surprisingly, after further addition of Sr to the glass structure, the X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) micrographs showed unexpected significant rod-like crystal fibers, and the major diffraction peaks of Sr(NO₃)₂, SrCO₃ and Sr₂Si₂O₄ became sharper and more apparent up to the final addition of Sr. The complicated and contradictory results underscore the need for better knowledge of how impurities act upon by growing rod-like crystals. In addition, totally understanding the effect of Sr on the morphology of samples from the bottom up is a daunting challenge.     

Physical properties of lead iron phosphate glasses containing Cr2O3

The influence of Cr₂O₃ on glass forming characteristics and physical properties of PbO-Fe₂O₃-P₂O₅ glasses has been investigated by Raman and Mössbauer spectroscopies, X-ray diffraction analysis (XRD), Differential Thermal Analysis (DTA), Scanning Electron Microscopy (SEM) and impedance spectroscopy. Glasses of the general composition xCr₂O₃-(28.3-x)PbO-28.7Fe₂O₃-43.0P₂O₅, 0 ≤ × ≤ 10, (mol%) were prepared by conventional melt-quenching technique. The compositions containing up to 4 mol% Cr₂O₃ formed fully amorphous samples and their Raman spectra show systematic increase in the fraction of orthophosphate Q⁰ units with increasing Cr₂O₃ content and O/P ratio.On the other hand, compositions containing 8 and 10 mol% Cr₂O₃ partially crystallized during cooling and annealing to Fe₇(PO₄)₆, Fe₂Pb₃(PO₄)₄ and Cr₂Pb₃(PO₄)₄. A high tendency for crystallization of these melts is related to the high O/P (> 4) and Fe²⁺/Fe_tot (≈ 0.60) ratios.Electrical conductivity of xCr₂O₃-(28.3-x)PbO-28.7Fe₂O₃-43.0P₂O₅, 0 ≤ × ≤ 10, (mol%) compositions is independent of Cr₂O₃ and controlled entirely by the polaron transfer between Fe²⁺ and Fe³⁺ ions.     

Influence of heat treatment on spectroscopic properties of Er in multicomponent ZrF4-ZnF2-AlF3-YF3-MF2 (M = Ca, Sr, Ba) based glass

Er³⁺ doped multicomponent fluoride based glass was prepared. These precursor fluoride glass samples were then heated using different schedules. Crystalline phase particles were successfully precipitated in the multicomponent fluoride glass samples after heat treatment. The influence of heat treatment on the spectroscopic properties of Er³⁺ in multicomponent fluoride based glass samples were discussed. Small changes of the Judd-Ofelt parameters Ω_i (i = 2, 4, 6) were found in multicomponent fluoride glass samples before and after heat treatment compared to oxyfluoride telluride glass. Preparation conditions used to produce transparent multicomponent fluoride glass ceramics doped with rare-earth ions are discussed.     

Structure and electrical conductivity of new Li2O-CeO2-B2O3 glasses

Fourier transformation infrared spectra, density and DC electrical conductivity of 30Li₂O · xCeO₂⋅(70 − x)B₂O₃ glasses, where x ranged between 0 and 15 mol%, have been investigated. The results suggested that CeO₂ plays the role of network modifier up to 7.5 mol%. At higher concentrations it plays a dual role; where most of ceria plays the role of network former. The density was observed to increase with increasing CeO₂ content. The effect on density of the oxides in the glasses investigated is in the succession: B₂O₃ < Li₂O < CeO₂. Most of CeO₂ content was found to be associated with B₂O₃ network to convert BO₃ into B O₄⁻ units. The contribution of Li⁺ ions in the conduction process is much more than that due to small polarons. The conductivity of the glasses is mostly controlled by the Li⁺ ions concentration rather than the activation energy for CeO₂ > 5 mol%. Lower than 5 mol% CeO₂ the conductivity is controlled by both factors. The dependence of W on BO₄⁻ content supports the idea of ionic conduction in these glasses.     

Ionic conductivity of Li2O-BaO-Bi2O3 glasses

Dc and ac conductivities of Li₂O-BaO-Bi₂O₃ glasses have been studied in a temperature range of 263-523 K and a frequency range of 10 Hz-2 MHz and have been compared with those of binary Li₂O-Bi₂O₃ glasses. The frequency dependent conductivity has been studied employing both the modulus and conductivity formalisms. We have observed small changes in the dc conductivity and its activation energy from those of the binary glass when content of BaO is small. However we have observed noticeable changes in the conductivity and the activation energy when BaO content is large. The significant changes in the values of the non-exponential parameter and the power-law exponent of the ac electrical properties have been observed due to introduction of BaO in the lithium bismuthate glasses. The existing relation between the power-law exponent and the non-exponential parameter was also violated in the present glass compositions.     

Crystallization behavior and microstructure of powdered and bulk ZnO-Al2O3-SiO2 glass-ceramics

The crystallization behavior of glass with the composition: 55.6 mol% SiO₂, 22.8 mol% Al₂O₃, 17.7 mol% ZnO and 3.84 mol% of TiO₂ as nucleating agent and with different particle sizes has been studied by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and tranmission electron microscopy (TEM). In glass powders two crystalline phases: zinc-aluminosilicate s.s. with high-quartz structure, Zn_x/2Al_xSi_3−xO₆, (x varies dependent on heat-treatment temperature) and gahnite are formed. The ratio of these phases depends on particle sizes. In bulk glass, however, gahnite is the sole crystalline phase. The composition of initially formed zinc-aluminosilicate s.s. was determined by Rietveld refinement of XRD patterns to be Zn_0.69Al_1.38Si_1.62O₆. With temperature increase, the amount of zinc-aluminosilicate s.s decreased with simultaneous reduce of zinc and aluminum incorporated in the structure. Eventually at 1423 K almost pure high-quartz structure was formed. The activation energies of zinc-aluminosilicate s.s. and gahnite crystallization were determined by non-isothermal method to be 510 ± 18 and 344 ± 17 kJ mol⁻¹, respectively. The latter value matches well with those cited in literature for crystal growth of gahnite in similar glasses. That is attributed to the fact that the high-quartz structure acts as a precursor for gahnite crystallization.     

Thermal and some physical properties of glasses in the La2O3−CaO−B2O3 ternary system

Glasses in the La₂O₃−CaO−B₂O₃ ternary system were studied. The glass forming range as determined by the appearance of the annealed cast was found to match previously published findings. Clear glasses were formed in the composition range of 5.7−19.1 mol% La₂O₃ with constant B₂O₃ content of 71.4 mol%, and in glasses of constant La₂O₃:CaO ratio of 1:4 with B₂O₃ content in the range of 71.4-55.0 mol%. The non-linear optical crystalline phase La₂Ca₂B₁₀O₁₉ was crystallized from the clear glasses after heat treatments, as determined by powder XRD. Two types of the LaBO₃ crystalline phases were detected in the partially and the fully crystallized glass compositions outside the glass forming range. Data are reported for the glass transition temperature (T_g), dilatometric softening point (T_d), linear coefficient of expansion (α), onset crystallization temperature (T_x), exothermal peak temperature (T_P), density (ρ) and index of refraction (n_D) in the clear glasses.     

Multinuclear NMR study of phosphosilicate gels derived from POCl3 and Si(OC2H5)4

Solid state ¹H, ²⁹Si and ³¹P MAS NMR have been used to investigate the microstructure of phosphosilicate gels prepared by a modified sol-gel method involving hydrolysis of silicon precursors in a solely aqueous environment at 50 °C. Gels with molar compositions 5, 10, 20 and 30 mol% P₂O₅ in P₂O₅-SiO₂ were studied. After drying to 400 °C the gels have very similar structures formed by a siloxane framework containing silanol groups and trapped molecules of orthophosphoric acid together with a very small amount, of pyrophosphoric acid. Unlike the gel samples previously synthesized by the hydrolysis of the silicon precursor in alcoholic solution at room temperature, the co-polymerization of phosphorus and silicon is much reduced. Although co-polymerization increases with phosphorus content, it still represents less than 50% of the phosphorus in the 30 mol% P₂O₅ gel. Furthermore there is no evidence for six-coordinated silicon in the glassy matrix.     

Thermodynamic mixing properties of liquids in the system Na2O-SiO2

Enthalpies of fusion have been measured by differential scanning calorimetry for a Na₂O-SiO₂ system at 50, 66.6, and 74.4 mol% SiO₂. Enthalpies of mixing of liquids obtained from different calorimetry techniques are critically evaluated. The data on calorimetric enthalpy, activity of Na₂O, cristobalite liquidus, and immiscibility gap are used to determine the enthalpy and entropy of mixing of sodium-silicate liquids are determined as a function of composition by the least squares method. The derived mixing properties are based only on the experimental data and are independent of any assumption about the structure and chemical species in liquids. The enthalpy of mixing has a minimum value of −120 kJ/mol at 35-40 mol% SiO₂ and is convex upward around 80-90 mol% SiO₂. The entropy of mixing have a maximum value of + 6 J/K-mol at 75 mol% SiO₂, and it decreases with the SiO₂ content to −5 J/K-mol at 40 mol% SiO₂. This decrease in entropy can be accounted for by ideal mixing of Q⁴, Q³, and Q^{0 + 1 + 2} (= Q⁰ + Q¹ + Q²) species in the liquids and is responsible for the negative temperature dependence of the partial molar Gibbs energy of mixing of Na₂O, observed in activity measurements. Comparison of the present results with previous values suggests that a quasi-chemical model and the Adam-Gibbs model overestimate the configurational entropy of mixing of liquids.