Phase separation, crystallization and leaching of microporous glass ceramics in the CaO-TiO2-P2O5 system

Microporous glass ceramics belonging to the CaO-TiO₂-P₂O₅ system were prepared with the assumption of a 2:1 mole ratio for β-Ca₃(PO₄)₂:CaTi₄(PO₄)₆, the anticipated crystalline phases in the end product. The glasses formulated according to the above composition were melted and cast onto a steel mold and were crystallized to glass ceramics containing the above phases. Dilatometric/differential thermal analysis (DTA) techniques were utilized to determine the appropriate phase separation-nucleation and crystallization temperatures. The crystalline products and resulting microstructures in various stages of process were determined and observed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). By leaching the resulting glass ceramics in HCl, β-Ca₃(PO₄)₂ was dissolved out leaving a porous skeleton of CaTi₄(PO₄)₆. It was found that the volume porosity, specific surface area and mean pore diameter of microporous glass ceramics can be managed through the proper selection of heat treatment conditions. In the optimized conditions for fabricating glass ceramics of minimum mean pore size the values of 41 ± 4%, 26 ± 3 m²/g and 14.3 ± 2 nm were obtained for porosity, surface area and pore diameter respectively.     

Glass formation in the MoO3–Nd2O3–La2O3–B2O3 system

In MoO₃–Nd₂O₃–B₂O₃ and MoO₃–Nd₂O₃–La₂O₃–B₂O₃ systems, glasses were obtained in the region between 20 and 30 mol% Ln₂O₃. A liquid-phase separation region was observed near the MoO₃–B₂O₃ side up to 20 mol% Ln₂O₃ (La, Nd). The amorphous phases were characterized by X-ray diffraction (XRD), differential thermal analysis (DTA), UV–VIS and infrared spectroscopy (IR). According to DTA data B₂O₃-rich glasses are stable up to 630 °C while glasses rich in MoO₃ are stable up to 430 °C. The glasses are transparent in the visible region. Structural models for the glasses network were suggested on the basis of IR spectral investigations. It was established that BO₃ (1380 cm⁻¹), BO₄ (1100–950 cm⁻¹) and MoO₄ (860 cm⁻¹) groups build up the glass network. MoO₆ units (band at 880 cm⁻¹) together with BO₃ units participate in the formation of the glass network with a high MoO₃ content (80–90 mol%).     

Structural analysis and devitrification of glasses based on the CaO-MgO-SiO2 system with B2O3, Na2O, CaF2 and P2O5 additives

Glasses, whose basic composition was based on the CaO-MgO-SiO₂ system and doped with B₂O₃, P₂O₅, Na₂O, and CaF₂, were prepared by melting at 1400 °C for 1 h. Raman and infrared (IR) spectroscopy revealed that the main structural units in the glass network were predominantly Q¹ and Q² silicate species. The presence of phosphate and borate units in the structure of the glasses was also evident in these spectra. X-ray analysis showed that the investigated glasses devitrified at 750 °C and higher temperatures. The crystalline phases of diopside and wollastonite dominated, but weak peaks, assigned to akermanite and fluorapatite, were also registered in the diffractograms. The presence of B₂O₃, Na₂O, and CaF₂ had a negligible influence on the assemblage of the crystallized phases, but it caused a reduction of crystallization temperature, comparing to similar glasses of the CaO-MgO-SiO₂ system.     

Preparation of dye-loaded SiO2 nanoparticles

A room temperature method for the encapsulation of pyrene in SiO₂ nanoparticles is described. The relation between alkoxysilane surfactant chain length, reactant molar ratios and the uptake of dye, sample morphology, photophysical properties, and the ability of the silicate matrix to protect the encapsulated dye was examined. The synthesis can easily be adapted for the encapsulation of other hydrophobic and thermolabile substances, and used in the development of nanostructured optically active coatings, films and monoliths.     

Luminescence behavior of Er ions in glass-ceramics containing CaF2 nanocrystals

The upconversion luminescence and near infrared luminescence of the Er³⁺ ions in transparent oxyfluoride glass-ceramics containing CaF₂ nanocrystals have been investigated. The formation of CaF₂ nanocrystals in the glass-ceramics was confirmed by XRD. The oscillator strengths for several transitions of the Er³⁺ ions in the glass and glass-ceramics have been obtained and then the Judd-Ofelt parameters were calculated. The split near infrared emission peaks of the Er³⁺ ions in the glass-ceramics can be observed because the Er³⁺ ions have been incorporated into crystalline environment of the CaF₂ nanocrystals. The upconversion luminescence intensity of Er³⁺ ions in the glass-ceramics increased significantly with increasing heat treated time. The transition mechanism of the upconversion luminescence has been ascribed to a two-photon absorption process.     

Structural peculiarities, and electrical and optical properties of 70TeO2·30PbCl2 glasses doped with Pr, prepared in Pt or Au crucibles

The influence of crucibles (Au or Pt) on the structure, electrical, dielectric and optical properties of 70TeO₂·30PbCl₂ glasses doped with Pr³⁺ added as a metal, chloride, or oxide, in concentrations of 500–1500 wt-ppm, is reported. The dc conductivity of ‘pure’ glasses prepared in Au crucibles is two orders of magnitude higher than that of those prepared in Pt crucibles. Upon doping, the dc conductivity of glasses prepared in Pt and Au crucibles increases or decreases, respectively. The static relative permittivity is equal to 33 ± 2. In the range of 640–700 nm, six photoluminescence (PL) peaks were observed, at 641.5, 647.1, 652.4, 660.8, 662.9, and 664.5 nm. In the range of 200–1200 cm⁻¹, seven Raman scattering (RS) peaks were observed at 184, 217, 321, 468, 654, 735 cm⁻¹, and a small peak at 650 cm⁻¹. Both spectra were deconvoluted using symmetrical Gaussian functions. Relative intensities of PL and RS bands depend on the concentration and chemical form of Pr³⁺ and on the material of the crucible. However, positions of these bands are independent of these conditions.     

Glass formation and non-isothermal crystallization of Zr62.5Al12.1Cu7.95Ni17.45 bulk metallic glass

Glass forming ability (GFA) and non-isothermal crystallization kinetics of Zr_62.5Al_12.1Cu_7.95Ni_17.45 bulk metallic glass were investigated. Its critical dimension is up to 7.5 mm and its critical cooling rate is less than 40 K s⁻¹, indicating its better GFA. It manifests two crystallization procedures and the second crystallization peak is more sensitive to heating rate than the first crystallization peak. The glass transition and crystallization both have remarkable kinetics effects. The apparent activation energies derived from the Kissinger plots are 175.24 ± 27.59 KJ mol⁻¹ for glass transition E_g, 212.84 ± 15.84 KJ mol⁻¹ for onset crystallization E_x, 230.51 ± 23.85 KJ mol⁻¹ for the first crystallization peak E_p1 and 124.85 ± 15.15 KJ mol⁻¹ for the second crystallization peak E_p2.     

Structural and transport properties of quaternary glass system: LiF-Li2O-SrO-Bi2O3

Bismuth based glasses containing LiF, Li₂O and SrO were investigated by different physical, spectroscopic and transport techniques. The results show that density of the glass system increases whereas glass transition temperature decreases with increase in LiF content. The decrease in glass transition temperature is attributed to the entry of the fluoride ions into the glass network mainly substitutionally in place of oxygen ion. The increase in dc electrical conductivity in the present glasses with increase in the fluorine ions is due to the mixed contribution of the positively charged lithium cations throughout the glass network and the negatively charged fluorine, which may act as impurity and/or as terminal non-bridging halide ion. Infrared and Raman spectroscopic results indicate that the glass network consists of BiO₆ octahedral and BiO₃ pyramidal units.     

Glass preparation and temperature-induced crystallization in multicomponent B2O3-PbX2-PbO-Al2O3-WO3-Dy2O3 (X = F, Cl, Br) system

Multicomponent lead borate glasses modified by PbX₂ (X = F, Cl or Br) were examined. For the first time, lead tungstate PbWO₄ crystallites dispersed into glass matrices were successfully obtained from controlled crystallization. Excitation by 310 nm line leads to broad blue luminescence related to the radiative transition which occurred in the PbWO₄ crystallites. It was found that halogen X ions (X = F, Cl or Br) were also incorporated in the distorted crystal system of PbWO₄. It was proved by results obtained from X-ray diffraction as well as luminescence measurements.     

Crystallization and glass transition kinetics in Cu ion substituted Cux-Ag1 − xI-Ag2O-V2O5 superionic glasses

Crystallization kinetics and thermal properties in superionic glasses Cu_xAg_1 − xI-Ag₂O-V₂O₅ for x = 0.1-0.3 have been thoroughly investigated. X-ray diffraction and differential scanning calorimetry measurements confirm the precipitation of at least three compounds during crystallization, viz. AgI, Ag₄V₂O₇ and Ag₈I₄V₂O₇. The activation energies for structural relaxation (E_s) and crystallization (E_c) obtained using Moynihan and Kissinger formulation exhibit interesting trends with CuI substitution. The E_s value decreases with CuI substitution in the system. Further, the E_c values corresponding to precipitation of Ag₄V₂O₇ and Ag₈I₄V₂O₇ exhibit increasing trend, whereas, for that of AgI precipitation a decreasing trend with CuI content. The Avrami parameter calculated from Augis-Bennett method and Ozawa equation suggests predominantly surface crystallization in the glassy system. The electrical conductivity-temperature (σ-T) cycles interestingly demonstrate increasing precipitation of AgI with CuI content in the glass matrix.     

Structure and properties of glasses in ZnO-P2O5-TeO2 system

Glasses in the ternary ZnO-P₂O₅-TeO₂ system were prepared and studied in two compositional series (100 − x)[0.5ZnO-0.5P₂O₅]-xTeO₂ (X-series) and 50ZnO-(50 − y)P₂O₅-yTeO₂ (Y-series) within the concentration range of x = 0-60 and y = 0-40 mol% TeO₂. Their structure was studied by Raman and ³¹P MAS NMR spectroscopies. The incorporation of TeO_x units into the structural network is associated with the depolymerisation of phosphate chain structure as revealed by both methods. At a high TeO₂ content isolated PO₄ tetrahedra are formed in the structure of glass series Y, while diphosphate O₃P-O-PO₃ groups are present in the structure of the glass series X. In the structure of glass series Y tellurium atoms form predominantly TeO₃ trigonal pyramids, whereas in the X glass series TeO₄ trigonal bipyramids prevail in the glass structure. The addition of TeO₂ to the parent zinc metaphosphate glass results in a decrease of glass transition temperature in both compositional series associated with the replacement of stronger P―O bonds by weaker Te―O bonds.     

Peculiarities of photoluminescence excited by 157 nm wavelength F2 excimer laser in fused and unfused silicon dioxide

Photoluminescence (PL) spectra and kinetics of high purity amorphous silicon dioxide with ultra low hydroxyl content is studied under the excitation by F₂ excimer laser (157 nm wavelength) pulses. Materials synthesized in the SPCVD plasma chemical process are studied before and after fusion. Two bands are found in the PL spectra: one centered at 2.6–2.9 eV (a blue band) and the other at 4.4 eV (a UV band). Luminescence intensity of unfused material is found to increase significantly with exposure time starting from a very small level, whereas in fused counterpart it does not depend on irradiation time. Both bands show complicated decay kinetics, to which add exponential and hyperbolic functions. The UV band of the unfused material is characterized by decay with exponential time constant τ  4.5 ns and hyperbolic function t⁻ⁿ, where n = 1.5 ± 0.4. For the blue band the hyperbolic decay kinetics with n  1.5 extends to several milliseconds, gradually transforming to the exponential one with τ = 11 ± 0.5 ms. In fused glass relative contribution of the fast component to the UV band is small whereas for the blue one it is great, that allows one to more accurately determine the hyperbolic law factor n = 1.1 ± 0.1 typical for tunneling recombination. Simultaneous intracenter and recombination luminescence, the later occurring with the participation of laser radiation induced defects, add particular features to the decay kinetics. Spectra of the above luminescence processes are different. A less sharp position of bands is associated with the recombination luminescence. The origin of the observed PL features we attribute to the presence of oxygen deficient centers in glass network in the form of twofold coordinated silicon. Such centers being affected by network irregularities can be responsible for the recombination PL component. A great variety of network irregularities is responsible for centers’ structural inequivalence, which causes a non-uniform broadening of PL spectral and kinetic parameters.     

Effect of heat-treatment condition on crystallization behavior and thermal expansion coefficient of Li2O-ZnO-Al2O3-SiO2-P2O5 glass-ceramics

Utilizing P₂O₅ as nucleation agent, a Li₂O-ZnO-Al₂O₃-SiO₂ glass was prepared by conventional melt quenching technique and subsequently converted to glass-ceramics with different crystal phases. During the processing, two-step heat-treatments including nucleation and crystallization were adopted. The effects of heat-treatment on the crystal type, the microstructure and the thermal expansion behavior of the glass-ceramics were studied by means of differential scanning calorimetry, X-ray powder diffraction analysis, scanning electron microscopy and thermal expansion coefficient tests. It was shown that the crystallization of occurred after the glass was treated at 580 °C. As the temperature increased from 580 °C to 630 °C, cristobalite and were identified as main and second crystal phases, respectively, in the glass-ceramic. An increase in the temperature to 700 °C, the β-quartz solid solution in the glass-ceramic accompanied by a decrease in cristobalite content. The transformation from to γ₀-Li₂ZnSiO₄ took place from 700 °C to 750 °C. The resulting crystallization phases in the glass-ceramics obtained at the temperature higher than 750 °C were β-quartz solid solution and γ₀-Li₂ZnSiO₄. The glass-ceramics containing or β-quartz solid solution crystal phase possessed a microstructure formed by the development of dendritic crystals. The thermal expansion coefficient of the glass-ceramics varied from 36.7 to 123.8 × 10⁻⁷ °C⁻¹ in the temperature range of 20-400 °C, this precise value is dependent on the type and the proportion of the crystalline phases presented.     

Bioactive glasses in the system CaO-B2O3-P2O5: Preparation, structural study and in vitro evaluation

Glasses in the system x B₂O₃(1 − x) [y CaO P₂O₅], (x = 0, 0.1, 0.2, 0.3, y = 2, 2.6, 3, 4, 5) have been prepared by fast quenching of high temperature melts. The presence of B₂O₃ affected the glass forming ability, allowing the preparation of calcium phosphate glasses with y ? 2.6. The structure of glasses was analyzed by μ-Raman and infrared spectroscopy. The analysis indicated that the glass network is dominated by highly charged species from phosphate tetrahedra with 3 (pyro) or 4 (ortho) NBOs, while the boron atoms are incorporated mainly in 3 coordinated sites in the form of B∅₃ or B∅₂O⁻ units. A small fraction of units was also evident from the spectra analysis of glasses with high CaO content. All calcium borophosphate glasses exhibited bioactivity after soaking in SBF solution within a few days. This was observed by μ-Raman and SEM microscopy, while XRD patterns clearly revealed growth of hydroxyapatite phase. The presence of boron in the glass network has a catalytic effect at favoring bioactivity of the otherwise bioinert calcium phosphate glasses.     

Structural and electrical properties of Germanium-doped Sb70Te30 eutectic thin films

Ge-doped Sb₇₀Te₃₀ eutectic films show high potential for high transfer rate recording and non-volatile memory applications. Their potential applications are based on the difference in optical and electrical properties between the crystalline and amorphous phases. However, the structure and crystallization mechanism of such films is not yet well understood.The aim of this work is to study the amorphous-to-crystalline phase transformation mechanism in eutectic thin films of pure Sb₇₀Te₃₀ and doped with 2, 5 and 10 at% of Ge. Results of isokinetics and isothermal annealing were carried out using various techniques: four-probe electrical, optical reflectance and X-ray measurements.The results of optical and electrical measurements of Ge doped Sb₇₀Te₃₀ eutectic films showed that the addition of Ge increases both, the crystallization temperature and the effective activation energy of crystallization and that the mechanism of crystallization does not depend on Ge contents.In amorphous films, Ge acts as impurity center and does not affect the optical band gap value, but decreases the pre-exponential factor in the thermally activated conductivity. In crystalline films, Ge is probably incorporated into the Sb₇₀Te₃₀ structure and Ge vacancy are responsible for p-type metallic conduction, which increases with increasing the Ge content.     

Role of nickel ion coordination on spectroscopic and dielectric properties of ZnF2-As2O3-TeO2:NiO glass system

20ZnF₂-30As₂O₃-(50 − x)TeO₂:xNiO (0 ≤ x ≤ 2.0) glasses were synthesized. The glasses were characterized by X-ray diffraction, scanning electron microscopy, EDS and DSC techniques. A variety of properties, i.e. optical absorption, infrared, magnetic susceptibilities and dielectric properties (constant ?′, loss tan δ, a.c. conductivity σ_ac over a wide range of frequency and temperature) of these glasses have been carried out. The analysis of results of all these studies has indicated that the nickel ions occupy both octahedral and tetrahedral positions and the gradual increase of NiO content in the glass matrix causes growing proportions of Ni²⁺ ions that occupy octahedral positions. The luminescence spectra of these glasses have exhibited a broad emission band in region 1200-1450 nm identified due to ³T₂(3F) → ³A₂(3F) octahedral transition of Ni²⁺ ions. The luminescence efficiency and cross section have been found to be the highest for the glass containing highest concentration of NiO. Finally it is concluded that the higher the concentration of octahedrally positioned Ni²⁺ ions, the higher is the luminescence efficiency.     

Crystallization behavior in a highly driven marginal glass forming alloy

Al₉₀Sm₁₀, a marginal glass former, was rapidly solidified using Cu-block single roller melt spinning at wheel speeds of 30 and 40 m/s. The product phases of rapid solidification were identified and analyzed using high energy synchrotron X-ray diffraction (HEXRD), high resolution transmission electron microscopy, and atom probe tomography. The as-quenched structure consists of a saturated amorphous phase and nanocrystalline Al with typical length scale of about 5 nm. The appearance of a pre-peak on HEXRD diffraction patterns and a low activation energy for first crystallization as determined using the Kissinger and Ozawa methods indicate some local ordering in the amorphous phase. The devitrification phase transformation path was determined using in situ high energy synchrotron radiation. Three phases, MS1, H1, and Al₄Sm, were identified during decomposition of the amorphous phase. MS1, H1 and Al₄Sm are cubic, hexagonal and orthorhombic metastable phases, respectively.     

Thermal stability and crystallization behavior of TiO2 doped ZBLAN glasses

ZBLAN glasses with the composition (in mol%) of (100 − x)(53 ZrF₄ + 19 BaF₂ + 5LaF₃ + 3AlF₃ + 20NaF) + xTiO₂ (x = 0, 1.0 and 2.0 mol%) were prepared using a conventional melting technique in dry nitrogen atmosphere. The thermal stability, glass-forming ability, and crystallization kinetics of the ZBLAN system as a function of the TiO₂ concentrations were investigated by Differential Scanning Calorimetry (DSC). Also, the crystalline phases were determined by X-ray Diffraction (XRD). Our study indicates that adding TiO₂ in a fluoride system improves the thermal parameters of the glass, which is interesting for applications as optical fiber.     

Glasses and glass-ceramics in the oxyfluoride ternary system Pb(PO3)2-WO3-PbF2

Glasses were prepared by the melt-quenching method in the ternary system Pb(PO₃)₂-WO₃-PbF₂ and doped with Er³⁺ in order to prepare luminescent transparent glass-ceramics. This work focused on thermal and structural characterization of tungsten lead-phosphate glasses and crystallization study for preparing transparent glass-ceramics. Thermal properties such as thermal stability and crystallization behavior upon heating were investigated by DSC in function of PbF₂ content. For low PbF₂ concentrations, only one crystallization peak due to Pb₃(PO₄)₂ is observed whereas samples containing more than 15% of PbF₂ present another exothermic event at lower temperatures related with precipitation of PbF₂, Pb₂P₂O₇ and Pb₂OF₂. Structural investigations by Raman spectroscopy suggest that PbF₂ modifies the tungsten-phosphate network through the formation of P―F and P―O―Pb bonds but the average network connectivity remains almost constant. A crystallization study has been performed by DSC to investigate the dominant crystallization mechanisms in these glasses and it has been established that Pb₃(PO₄)₂ is nucleated on the surface whereas PbF₂, Pb₂P₂O₇ and Pb₂OF₂ crystallize dominantly from the glassy bulk. Transparent glass-ceramics containing nanosized PbF₂ crystallites were also prepared by suitable heat-treatment on the glass sample containing 20% of PbF₂ and Raman microscopy of these glass-ceramics supports the crystallization mechanisms determined by DSC.     

Crystallization kinetics of the Zr61Al7.5Cu17.5Ni10Si4 alloy using isothermal DSC and TEM observation

The crystallization behavior and microstructure development of the Zr₆₁Al_7.5Cu_17.5Ni₁₀Si₄ alloy during annealing were investigated by isothermal differential scanning calorimetry, X-ray diffractometry and transmission electron microscopy. During isothermal annealing of the Zr₆₁Al_7.5Cu_17.5Ni₁₀Si₄ alloy at 703 K, Zr₂Cu crystals with an average size of about 5 nm were first observed during the early stages (30% crystallization) of crystallization by TEM. The Zr₂Cu crystal size increased with annealing time and attained an average size of 20 nm corresponding to the stage of 80% crystallization. In addition, the change in particle size with increasing annealing time exhibited a linear relationship between grain growth time and the cube of the particle size for the Zr₂Cu type crystalline phase. This indicates that the crystal growth of the Zr₆₁Al_7.5Cu_17.5Ni₁₀Si₄ alloy belongs to a thermal activated process of the Arrhenius type. The activation energy for the grain growth of Zr₂Cu is 155 ± 20 kJ/mol in the Zr₆₁Al_7.5Cu_17.5Ni₁₀Si₄ amorphous alloy. The lower activation energy for grain growth in compared to that for crystallization in Zr₆₅Cu₃₅ 440 kJ/mol crystal corresponds to the rearrangement of smaller atoms in the metallic glass, Al or Si (compare to Zr).