Surface crystallization of leucite in glasses

The aim of this paper was to study surface crystallization of leucite in glasses derived from an SiO₂-Al₂O₃-K₂O base glass in a comparative study with another glass based on SiO₂-Al₂O₃-MgO. Monolithic samples and glass powder of SiO₂-Al₂O₃-K₂O glass were studied and phase formations were determined by using scanning electron microscopy. Heterogeneous nucleation was promoted by seeding the surface of the monolithic glass samples with glass dust to produce a highly disordered crystal as the primary phase. In addition to leucite formation, growth of a highly symmetric, flat, almost two-dimensional crystal phase with controlled diffusion was also observed. In glass granules, leucite demonstrated rapid, almost dendritic growth, from the nucleating centers. Use of leucite ceramic as a restorative dental product is considered.     

Low expansion copper aluminosilicate glasses

The thermal expansion coefficients of Cu₂O---Al₂O₃---SiO₂ glasses have been measured. These glasses have very low expansion coefficients similar to that for SiO₂ glass, but their liquids temperatures are much lower. It was possible to reduce the liquids temperature by the addition of 2 mol% of Na₂O while maintaining low expansivity. In order to explain the low expansivity, the effects of cation size, valence, the Cu²⁺/Cu⁺ ratio, bond strength and phase separation were examined. Phase separation was observed in these glasses which probably consisted of a copper-rich dispersed phase and a network former-rich matrix phase. It was concluded that the overall expansion coefficients of the glasses were governed by the low expansion matrix phase.     

Diffraction studies of rare-earth phosphate glasses

A series of lanthanide oxides was incorporated in a vitreous phosphate host network. Molar constituents of the glasses were typically (La₂O₃)₁₀(R_xO_y)₁₀(Al₂O₃)₅(P₂O₅)₇₅. Each glass had a different lanthanide (R atom) from the series; La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er and the values of x and y depended on the valency of the rare-earth atom. Both X-ray and neutron diffraction were employed in examining their structures. The results indicate that the basic PO₄ tetrahedral unit remains unaltered with an average P–O distance of and predominant Q² linkages to its neighbouring units so as to form a continuous network while accommodating the included lanthanides. In accordance with this model, the average distance of rare-earth (comprising La and a second type of R atom) to oxygen decreased from 2.44 to 2.26 , a trend to be expected from the lanthanide contraction. The average oxygen coordination around the rare-earth was found to vary in the range of 6–8. With these average parameters, a small (74 atom) hand-built model was made to check the feasibility of constructing a continuous random network. Optical transmission measurements show all these glasses to absorb strongly in the UV region and to have marked absorption resonances in the visible region of 400–1000 nm except for the La, Ce, Eu, Tb containing glasses which have low or negligible absorption in the latter range.     

Crystallization behavior of rare-earth doped fluorochlorozirconate glasses

A series of fluorochlorozirconate (FCZ) glasses, each doped with a different rare-earth, was prepared and examined to determine thermal stability and activation energy, E_a, of the dopant dependent BaCl₂ crystallization. Non-isothermal differential scanning calorimetry (DSC) measurements were done to investigate the endothermic and exothermic reactions upon heat treatment of the glass samples. In comparison to the rare-earth free FCZ glass, significant changes in the Hruby constant, H_r, and E_a were found due to the addition of a rare-earth and also between the individual dopants.     

New evidence for tetrahedral triclusters in aluminosilicate glasses

The formation of thermodynamically stable 3/2-mullite (3 Al₂OAl₃·2 SiO₂) was investigated by scanning electron microscopy using reaction couples consisting of 2/1-mullite (2 Al₂O₃·1 SiO₂) plus SiO₂ glass, or Na₂O-SiO₂ glass, respectively. The mullite substrates were partially dissolved, thus leading to Al incorporation in the siliceous phases. In both reaction couples thin layers of stoichiometric 3/2-mullite form on the 2/1-mullite substrates. However, the major mullitization steps are different: The 2/1-mullite/SiO₂ reaction couple gives rise to 3/2-mullite crystallization within the bulk of the glass, whereas epitactic growth of c-axis orientated 3/2-mullite needles on the 2/1-mullite substrate was observed in the presence of Na₂O-SiO₂ glass. The differences in mullite nucleation were attributed to the existence or non-existence of tetrahedral triclusters in the as-reacted non-crystalline Al₂O₃-SiO₂ and Na₂O-Al₂O₃-SiO₂ phases, respectively. Triclusters of (Si,Al)O₄-tetrahedra in the Al₂O₃-SiO₂ glass may act as nuclei for 3/2-mullite crystallization in the bulk of the glass since these structural units also occur in mullite. In Na₂O-Al₂O₃-SiO₂ glasses triclusters are absent, and epitactical 3/2-mullite formation on the mullite substrate becomes more favorable energetically.     

Characterization of thermo-optical and mechanical properties of calcium aluminosilicate glasses

In this work several different compositions of CaO:Al₂O₃:SiO₂ were prepared under vacuum atmosphere to study the glass forming ability of this system as a function of the SiO₂ content. Samples containing 25–45 wt% of Al₂O₃, 31–44 wt% of CaO, 14–39 wt% of SiO₂ and 4.1 wt% of MgO were prepared in graphite crucibles, for approximately 2 h at ∼ 1600 °C. The influence of silica content is discussed in terms of the mechanical properties, glass transition temperature, crystallization temperature, transmittance spectrum, refractive index, mass density, specific heat, thermal diffusivity, thermal conductivity and the temperature coefficient of optical path length change. The results reinforce the idea that these glasses are strong materials, having useful working-temperature range, good combination of thermal, mechanical and optical properties that could be exploited in many optical applications, in particular, as glass laser materials.     

Cl effects on structure of Zr and Ti alkali aluminosilicate glasses

Na-aluminosilicate glasses with Na/Al > 1 and added Ti or Zr have been analyzed by Raman spectroscopy to determine the effect of Cl on glass structure. Spectra of Ti-bearing glasses show a significant difference between the Cl-free and the Cl-bearing composition. The Cl-free glass spectrum contains a strong, asymmetric peak at 900 cm⁻¹ which is associated with Ti in fivefold coordination. This peak is shifted to higher frequency and becomes more symmetric with the addition of 0.3 wt% Cl. Deconvolution of the high-frequency waveband indicates differences between spectra are the result of a contribution from a peak at 945 cm⁻¹ resulting from Ti–O vibrations in fully polymerized titanate tetrahedra. It is proposed that addition of Cl destabilizes ^[5]Ti in favor of tetrahedral coordination as a result of competition between Cl and titanate groups for alkalis. The spectra of Zr-bearing glasses show a strong peak at 980 cm⁻¹ which is not seen in spectra of the base glass, indicating a vibrational mode associated with a zirconosilicate structure. There is no discernible difference between the Raman spectra of Zr-bearing glasses with and without added Cl, indicating that the local structure around Zr is insensitive to the presence of Cl.     

Melt crystallization of zinc alkali phosphate glasses

Melt crystallization of two zinc alkali phosphate glasses was studied with X-ray diffraction (XRD) experiments to accelerate efforts to melt process these glasses with organic polymers. The inorganic glasses differed markedly in chemical durability (water sensitivity) and crystallization rates. They were studied at room temperature prior to and after melt processing with XRD experiments and in situ at melt temperatures without flow in a novel differential scanning calorimeter/XRD apparatus. The glasses were found to be amorphous at room temperature and semi-crystalline above their glass-transition temperatures. Higher temperatures and shear (mixing) rates increased the crystallization rate of the glasses. The non-durable (water-sensitive) glass was observed to contain significant levels of crystalline matter after melt processing at 400°C. This process-induced crystallization of the glasses must be controlled, possibly during processing and/or glass formulation, otherwise it may lead to formation of unwanted phase-separated defects in the glass. If high levels of the crystalline matter are present during melt processing, they may lead to irreversible plugging of the processing equipment.     

Structural characterization of lanthanum aluminosilicate glasses by 29Si solid-state NMR

We investigate the network structures of LaSiAlO glasses by ²⁹Si magic-angle-spinning (MAS) nuclear magnetic resonance (NMR). Their compositions span most of the glass-forming region of the ternary La₂O₃Al₂O₃SiO₂ system at 1600 °C. The ²⁹Si NMR resonances narrow and become progressively deshielded when Al substitutes for Si in the network, as well as for increasing La-content of the glass, which leads to network depolymerization. We compare experimental and calculated center of gravities of the ²⁹Si NMR peaks, the latter generated from different simplified models for the distributions of Al and Si as well as bridging oxygen (BO) and non-bridging oxygen (NBO) atoms over the networks. The data do not permit accurate quantifications and may only be interpreted in limiting scenarios. However, they indicate that both distributions are essentially randomized, implying a clear deviation of the Al/Si ordering from that according to a Loewenstein Al-avoidance, coupled with a nearly uniform partitioning of the NBO atoms between Al and Si tetrahedra.     

Local Al site distribution in aluminosilicate glasses by Al MQMAS NMR

Coordination and local environment around Al in glasses and liquids is a long-standing question, which has been a controversial issue in geochemistry and glass science. Nuclear magnetic resonance at high-field (750 MHz) was employed to investigate the geochemically and industrially important CaO-Al₂O₃-SiO₂ system. We show that Al remains mainly in tetrahedral position in glasses, however, the presence of five-fold coordinated aluminum is the general rule throughout the ternary CaO-SiO₂-Al₂O₃ system, except for the low silica percalcic region. The proportion of five-fold (Al^V) and six-fold (Al^VI) coordinated Al was quantified to determine the effects of composition overall the peralkaline part. Moreover our results indicate that Al may occupy more polymerized positions than Si. These two findings do put new questions to the modeling/understanding of these glasses and their parent liquids.     

Structure of rare-earth phosphate glasses by X-ray and neutron diffraction

Previous diffraction studies of the structures of rare-earth phosphate glasses (R₂O₃)_x(P₂O₅)_1−x are extended to glasses with smaller R³⁺ ions with R = Sm, Gd, Dy, Er, Yb, Y for x = ∼0.25 and with R = Nd, Sm, Gd for x = ∼0.15. Parameters for the P–O, R–O and O–O first-neighbor peaks were obtained by Gaussian fitting. P–P and R–P distances were estimated from the positions of peak maxima. Effects of residual silica or alumina contents present as a result of glass processing were taken into account for selected samples. The P–O coordination number, N_PO, and the P–O, O–O, P–P distances are consistent with the presence of phosphate tetrahedra and are insensitive to the R species and the R₂O₃ content. Rare-earth coordination numbers, N_RO, decrease from ∼8 to ∼6.5 when x is increased from ∼0.15 to ∼0.25. N_OO and N_PP decrease with increasing R₂O₃ content indicating the network disintegration. The numbers N_RO of the metaphosphate glasses (x = ∼0.25) decreases from ∼7 to ∼6 when R is changed from La to Yb. This change is also indicated by the behavior of the R–O distances and by constant number densities of atoms. The decrease in N_RO with increasing R₂O₃ content is due to the reduction in the number of terminal O (O_T) available for coordination of the R³⁺ ions (six at metaphosphate composition). Especially for smaller R³⁺ ions sharing O_T between two R sites is not favored. The decrease by ∼0.04 nm of the prominent R–R first-neighbor distance with a change of R from La to Yb at the metaphosphate composition is indicated by a shift to higher magnitude of scattering vector of the shoulder occurring in front of the first main diffraction peak.     

Emission and local structure of rare-earth ions in chalcogenide glasses

Local structures of rare-earth ions in Ge–Ga–S–CsBr glasses were investigated to understand the structural origin on the emission property enhancement. The frequency of the phonon vibration controlling the multiphonon relaxation was changed to 245 cm⁻¹ due to the formation of Ga–Br bonds with CsBr addition to sulfide glasses. Formation of this new chemical bond was also confirmed from the phonon side band spectra of Eu³⁺ ions. Analyses of the EXASF spectra proved that Tm³⁺ ions were surrounded by approximately seven S ions in Ge_0.25Ga_0.10S_0.65 glass but were coordinated by ∼6 Br ions in the glass with 10 mol% of CsBr.     

Defect-mediated self-diffusion in calcium aluminosilicate glasses: A molecular modeling study

The mechanism of self-diffusion in calcium aluminosilicate glasses is investigated at the atomistic level using molecular dynamics (MD) simulations. We study nine glass compositions having the fixed ratio R = [CaO]/[Al₂O₃] = 1 and the concentration of SiO₂ varied from 11.8 to 76.5 mol%. The diffusion coefficient is calculated for each composition at different temperatures from 300 to 6000 K in steps of 300 K. The self-diffusivities of the various elements are found to be close to each other in magnitude, signifying the cooperative nature of the atomic movement. Network “defects” such as miscoordinated cations, non-bridging oxygen, and oxygen triclusters are also studied as a function of temperature and composition. We find that the behavior of self-diffusion correlates well with the concentration of network defects. A model of self-diffusion in calcium aluminosilicate glasses is proposed where diffusion is considered as a defect-mediated process resulting from bond-switching reactions at high temperature.     

Thermophysical properties of Zr-Cu-Al metallic glasses during crystallization

The crystallization behavior of Zr-Cu-Al metallic glasses was studied using thermophysical property measurements. When the Zr content of Zr-Cu-Al metallic glass decreased from 65 at.% to 45 at.%, the thermal conductivity gradually increased and the maximum value obtained was the composition of Zr:Cu:Al = 50:39.3:10.7(at.%). These metallic glasses were not crystallized upon heat treatment below the glass transition temperature T_g, and the thermophysical properties of these metallic glasses were almost constant. In contrast, these metallic glasses started to crystallize upon heat treatment above T_g after a certain derived time, and their thermal conductivity increased with the crystallinity of the metallic glass.     

Phase separation and controlled crystallization of non-oxide glasses

This paper reviews the experimental results associated with the phase separation and controlled crystallization of non-oxide glasses, mainly chalcogenide glasses and ZrF₄-based fluoride glasses. Experiments demonstrate that the phase separation is not always the precursor of the glass-ceramic process. It has been found that some non-oxide glasses could be converted into glass ceramics without phase separation. Different mechanisms of controlled crystallization of non-oxide glasses are discussed.     

Sintering and crystallization of titanium-containing lead borate glasses

The sintering and crystallization of glass powders with chemical composition 47 PbO—38 B₂O₃—15 TiO₂ (mole %) was investigated under non-isothermal conditions by shrinkage measurements, differential thermo-analysis (DTA), X-ray diffraction (XRD), dielectric measurement and positron annihilation (Doppler broadening). The correlation between changes of macroscopic properties and positron annihilation results recommends this method for the detection of structural changes in glasses.     

Structural order and crystallization of an iron-rich aluminosilicate liquid under oxidizing condition

An iron-rich aluminosilicate liquid is studied in different atmospheres by using differential scanning calorimetry. The results show that the oxidation state of iron and the maximum temperature of the scan have an effect on the liquid structure and on the crystallization behavior of the liquid during both cooling and reheating processes. Increase in Fe²⁺/Fe³⁺ enhances crystallization and favors formation of a stable crystal structure. The structural order conserved in the liquid is an intrinsic phenomenon, which is not related to the oxidation state of iron.