The Effect of Glass Structure on the Luminescence Spectra of Sm3+-Doped Aluminosilicate Glasses.

Peralkaline Sm3+-doped aluminosilicate glasses with different network modifier ions (Mg2+, Ca2+, Sr2+, Ba2+, Zn2+) were investigated to clarify the effect of glass composition and glass structure on the optical properties of the doped Sm3+ ions. For this purpose, the Sm3+ luminescence emission spectra were correlated with the molecular structure of the glasses derived by molecular dynamics (MD) simulations. The different network modifier ions have a clear and systematic effect on the peak area ratio of the Sm3+ emission peaks which correlates with the average rare earth site symmetry in the glasses. The highest site symmetry is found for the calcium aluminosilicate glass. Glasses with network modifier ions of lower and higher ionic radii show a notably lower average site symmetry. The symmetry could be correlated to the rare earth coordination number with oxygen atoms derived by MD simulations. A coordination number of 6 seems to offer the highest average site symmetry. Higher rare earth coordination probabilities with non-bridging oxygen result in an increased splitting of the emission peaks and a notable broadening of the peaks. The zinc containing glass seems to play a special role. The Zn2+ ions notably modify the glass structure and especially the rare earth coordination in comparison to the other network modifier ions in the other investigated glasses. The knowledge on how glass structure affects the optical properties of doped rare earth ions can be used to tailor the rare earth absorption and emission spectra for specific applications.

Phase stability determination of negative thermal expansion silicates by theory and experiment.

Materials that exhibit zero thermal expansion have numerous applications, ranging from everyday ceramic hobs to telescope mirrors to devices in optics and micromechanics. These materials include glass ceramics containing crystal phases with negative thermal expansion in at least one crystallographic direction, such as Ba1-xSrxZn2-2yMg2ySi2O7 solid solutions. However, the volume increase associated with the martensitic phase transformation in these crystals often hinders their use as zero thermal expansion materials at operating temperatures near the transition temperature Tt. Here, an approach to rapidly predict Tt of such materials as a function of chemical composition based on a combination of density functional theory simulations and experiments has been developed and applied to Ba1-xSrxZn2-2yMg2ySi2O7. Its central element is the modeling of free energy as a function of temperature and chemical composition using a composition-dependent Debye model augmented by an empirical correction, which incorporates the effects of anharmonic lattice vibrations. This approach provides Tt predictions with an estimated uncertainty of about ±100 K, which is similar to the accuracy of computationally much more demanding simulations of polymorphous phase transitions. In addition, this approach allows computationally efficient determination of the chemical compositions at which the Ba1-xSrxZn2-2yMg2ySi2O7 phase with the desired thermal properties will be formed during synthesis, facilitating the targeted design of zero thermal expansion materials.

The Structure of Gd3+-Doped Li2O and K2O Containing Aluminosilicate Glasses from Molecular Dynamics Simulations.

Understanding the atomic structure of glasses is critical for developing new generations of materials with important technical applications. In particular, the local environment of rare-earth ions and their distribution and clustering is of great relevance for applications of rare earth-containing glasses in photonic devices. In this work, the structure of Gd2O3 doped lithium and potassium aluminosilicate glasses is investigated as a function of their network modifier oxide (NMO-Li2O, K2O) to aluminum oxide ratio using molecular dynamics simulations. The applied simulation procedure yields a set of configurations, the so-called inherent structures, of the liquid state slightly above the glass transition temperature. The generation of a large set of inherent structures allows a statistical sampling of the medium-range order of the Gd3+ ions with less computational effort compared to other simulation methods. The resulting medium-range atomic structures of network former and modifier ions are in good agreement with experimental results and simulations of similar glasses. It was found that increasing NMO/Al ratio increases the network modifier coordination number with non-bridging oxygen sites and reduces the overall stability of the network structure. The fraction of non-bridging oxygen sites in the vicinity of Gd3+ ions increases considerably with decreasing field strength and increasing concentration of the network modifier ions. These correlations could be confirmed even if the simulation results of alkaline earth aluminosilicate glasses are added to the analysis. In addition, the structure predictions generally indicate a low driving force for the clustering of Gd3+. Here, network modifier ions of large ionic radii reduce the probability of Gd-O-Gd contacts.

Thermomechanical properties of zero thermal expansion materials from theory and experiments.

Origin and composition dependence of the anisotropic thermomechanical properties are elucidated for Ba1-xSrxZn2Si2O7 (BZS) solid solutions. The high-temperature phase of BZS shows negative thermal expansion (NTE) along one crystallographic axis and highly anisotropic elastic properties characterized by X-ray diffraction experiments and simulations at the density functional theory level. Ab initio molecular dynamics simulations provide accurate predictions of the anisotropic thermal expansion in excellent agreement with experimental observations. The NTE considerably decreases with increasing Sr content x. This is connected with the composition dependence of the vibrational density of states (VDOS) and the anisotropic Grüneisen parameters. The VDOS shifts to higher frequencies between 0-5 THz due to substitution of Ba with Sr. In the same frequency range, vibrational modes contributing most to the NTE are found. In addition, phonon calculations using the quasi-harmonic approximation revealed that the NTE is mainly connected with deformation of four-membered rings formed by SiO4 and ZnO4 tetrahedra. The thermomechanical and vibrational properties obtained in this work provide the basis for future studies facilitating the targeted design of BZS solid solutions as zero or negative thermal expansion material.

Phase Separation and Nanocrystallization in KF-ZnF2-SiO2 Glasses: Lessons from Solid-State NMR.

In the present paper, we studied the structural evolution of the glass matrix and formation of crystalline fluoride phases for 15KF-15ZnF2-70SiO2 (glass A) and 25KF-25ZnF2-50SiO2 (glass B) glasses upon thermal treatment employing transmission electron microscopy, X-ray diffraction (XRD), and solid-state NMR. The first step marks a phase separation into an SiO2 rich phase and a phase enriched with Zn, K, and fluoride. As shown by XRD, depending on the nominal compositions, K2SiF6 (for 15KF-15ZnF2-70SiO2) and KZnF3 (for 25KF-25ZnF2-50SiO2) are found as the first crystalline phases being formed. Upon longer heat treatment, ZnF2 is additionally formed in both cases. Surprisingly, a significant amount of SiF62- units is detected employing 29Si-MAS and 29Si{19F}CPMAS-NMR spectroscopy even in the base glass, which is completely amorphous according to the X-ray results. The vast majority of Si, however, is found in an exclusive SiO4 environment as Q4, Q3, or Q2 units. The large fraction of nonbridging oxygens per SiO4 tetrahedron (ca. 0.7 for glass A and 0.65 for glass B) indicates quite large fluorine loss during glass synthesis (approx. 60-80%). Employing dipolar NMR techniques, i.e., 29Si-{19F}-REDOR (rotational echo double resonance) and 29Si{19F}CPMAS-NMR (cross polarization magic angle spinning), the presence of Si-F connectivity (in excess of the identified SiF62- units) could be ruled out. The observed differences in the 29Si-19F heteronuclear dipole couplings between the Si-Q4 and Si Q3 units-as determined by REDOR NMR-are compatible with the assumption of a core-shell structure with a mixed cation fluoride as the core and an SiO2-enriched shell.

Structure Prediction of Rare Earth Doped BaO and MgO Containing Aluminosilicate Glasses⁻the Model Case of Gd2O3.

The medium-range atomic structure of magnesium and barium aluminosilicate glasses doped with Gd2O3 as a model rare earth oxide is elucidated using molecular dynamics simulations. Our structure models rationalize the strong dependence of the luminescence properties of the glasses on their chemical composition. The simulation procedure used samples' atomic configurations, the so-called inherent structures, characterizing configurations of the liquid state slightly above the glass transition temperature. This yields medium-range atomic structures of network former and modifier ions in good agreement with structure predictions using standard simulated annealing procedures. However, the generation of a large set of inherent structures allows a statistical sampling of the medium-range order of Gd3+ ions with less computational effort compared to the simulated annealing approach. It is found that the number of Si-bound non-bridging oxygen in the vicinity of Gd3+ considerably increases with growing ionic radius and concentration of network-modifier ions. In addition, structure predictions indicate a low driving force for clustering of Gd3+, yet no precise correlation between the atomic structure and luminescence lifetimes can be conclusively established. However, the structure models provided in this study can serve as a starting point for future quantum mechanical simulations to shed a light on the relation between the atomic structure and optical properties of rare earth doped aluminosilicate glasses.

Growing Oriented Layers of Bi4Ti3O12 in Bi2O3/TiO2/SiO2/Nd2O3/Al2O3 Glass-Ceramics by Melt Quenching.

A glass melt with the composition 24Bi2O3/40TiO2/10SiO2/10Nd2O3/16 Al2O3 was prepared and rapidly quenched between two copper blocks (sample A). A part of this glass was subsequently crystallised at 800 °C for 8 h (sample B). For the preparation of another two samples, the melt was slowly cooled on a cooper plate (sample C) or cast into a graphite mould and subsequently thermally treated at 300 °C for 3 h (sample D). As shown by X-ray diffraction (XRD) and scanning electron microscopy (SEM) including energy dispersive X-ray spectroscopy (EDXS) and electron backscatter diffraction (EBSD) measurements, the rapidly cooled samples contained notable amounts of uncrystallised glassy phase next to the Aurivillius phase Bi4Ti3O12. The latter occurred in higher concentrations in all other samples and formed oriented layers. Minor concentrations of Bi2Al4O9 and Al2O3 were also detected in the microstructure.

The effect of TiO2 on nucleation and crystallization of a Li2O-Al2O3-SiO2 glass investigated by XANES and STEM.

Glass ceramics based on Li2O/Al2O3/SiO2 are of high economic importance, as they often show very low coefficients of thermal expansion. This enables a number of challenging applications, such as cooktop panels, furnace windows or telescope mirror blanks. Usually, the crystallization of the desired LAS crystal phases within the glasses must be tailored by a careful choice of crystallization schedule and type of nucleation agents to be used. The present work describes the formation of nanocrystalline TiO2 within an LAS base composition that contains solely TiO2 as nucleating agent. Using a combination of scanning transmission electron microscopy as well as X-ray absorption spectroscopy, it is found that a mixture of four- and six-fold coordinated Ti4+ ions exists already within the glass. Heating of the glass to 740 °C immediately changes this ratio towards a high content of six-fold coordinated Ti, which accumulates in liquid-liquid phase-separation droplets. During the course of thermal treatment, these droplets eventually evolve into nanocrystalline TiO2 precipitations, in which Ti4+ is six-fold coordinated. Thus, it is shown that the nucleation of nanocrystalline TiO2 is initiated by a gradual re-arrangement of the Ti ions in the amorphous, glassy matrix, from a four-fold towards a six-fold coordination.

Redox effects and formation of gold nanoparticles for the nucleation of low thermal expansion phases from BaO/SrO/ZnO/SiO2 glasses.

Glasses in the system BaO/SrO/ZnO/SiO2 containing 0.01 and 0.1 mol% gold were used to study the formation of gold nanoparticles with the aim to use them as nucleation agents. In order to promote gold clustering, the glasses were additionally doped with 0.5 mol% Sb2O3. Depending on the heat treatment schedule, Au particle sizes were in the range from 6 to above 50 nm. In contrast to many other gold ruby glass systems, the clustering is completely prevented by the absence of antimony; then the glasses remain colorless. Surprisingly, at higher temperatures, a re-dissolution of gold clusters was also observed, which now allows the formulation of a more comprehensive model concerning the redox and clustering behavior. This growth model is completed by the fact that a high gold concentration enables the stabilization of much smaller Au clusters. Mie theory with the aid of quantum confined size-dependent dielectric functions was successfully used to describe the optical behavior of the gold nanoparticles also for sizes below 10 nm. These results were confirmed using high resolution scanning transmission electron microscopy, including energy dispersive X-ray spectroscopy. It could also be shown that small gold particles up to a size of 50 nm are not effective as nucleating agents.

Structure and crystallization of SiO2 and B2O3 doped lithium disilicate glasses from theory and experiment.

Solid solutions of SiO2 and B2O3 in Li2O·2SiO2 are synthesized and characterized for the first time. Their structure and crystallization mechanisms are investigated employing a combination of simulations at the density functional theory level and experiments on the crystallization of SiO2 and B2O3 doped lithium disilicate glasses. The remarkable agreement of calculated and experimentally determined cell parameters reveals the preferential, kinetically controlled incorporation of [SiO4] and [BO4] at the Li+ lattice sites of the Li2O·2SiO2 crystal structure. While the addition of SiO2 increases the glass viscosity resulting in lower crystal growth velocities, glasses containing B2O3 show a reduction of both viscosities and crystal growth velocities. These observations could be rationalized by a change of the chemical composition of the glass matrix surrounding the precipitated crystal phase during the course of crystallization, which leads to a deceleration of the attachment of building units required for further crystal growth at the liquid-crystal interface.

The formation of nanocrystalline ZrO2 nuclei in a Li2O-Al2O3-SiO2 glass - a combined XANES and TEM study.

The high economic importance of glass ceramics based on Li2O/Al2O3/SiO2 (LAS) is mainly due to their low coefficients of thermal expansion (CTE), which make these materials suitable candidates for a number of applications. The exact mechanism of the crystallization processes in LAS glasses is still not fully understood. The present work focuses on the formation and development of nanocrystalline ZrO2 within an LAS base composition which contains only ZrO2 as nucleating agent. Using a combination of transmission electron microscopy and X-ray absorption spectroscopy techniques, the temporal evolution of the ZrO2 nanocrystal formation is described. It is found that the formation of ZrO2 is initiated by liquid-liquid phase separation droplets with high Zr content, which eventually evolve into the nanocrystalline ZrO2 precipitations. This process is accompanied by a gradual change of the coordination of the tetravalent Zr ions from sixfold in the glass to eightfold in the crystals. The diameters of the ZrO2 crystals stay well below 4 nm, even at late stages. The degree of crystallization at each step of the crystallization process is deduced, and from that, the Avrami coefficient n is determined to be n ≈ 1, which describes a barrier-limited crystal growth process.

Variable thermal expansion of glass-ceramics containing Ba1-xSrxZn2Si2O7.

Up to now, the thermal expansion behavior of multiphase glass-ceramics cannot be predicted reliably because of the nescience about the formation of the type and concentration of crystalline phases. In the system BaO-SrO-ZnO-SiO2, recently a new phase based on Ba1-xSrxZn2Si2O7 solid solutions was found, which exhibits unexpected low and highly anisotropic thermal expansion, which can be used for an adjustment of the thermal expansion properties. In the case of sealing materials for high-temperature reactors, the formation of this phase should be avoided. Hence, in this manuscript the concentration thresholds in which these solid solutions precipitate from glasses were determined. The phase analysis was correlated with the thermal expansion behavior of the glass-ceramics. Depending on the Ba/Sr-ratio of the glasses and the considered temperature range, the coefficients of thermal expansion of the glass-ceramics vary between 19.4·10-6 K-1 and 4.8·10-6 K-1. The concentration thresholds in which the as mentioned phases form via crystallization of glasses differ strongly from the literature values obtained via conventional ceramic mixed oxide route.

Surface Crystallization of a MgO/Y2O3/SiO2/Al2O3/ZrO2 Glass: Growth of an Oriented ß-Y2Si2O7 Layer and Epitaxial ZrO2.

The crystallization behavior of a glass with the composition 54.7 SiO2·10.9 Al2O3·15.0 MgO·3.4 ZrO2·16.0 Y2O3 is studied using X-ray diffraction (XRD), scanning electron microscopy (SEM) including electron backscatter diffraction (EBSD) and (scanning) transmission electron microscopy [(S)TEM] including energy-dispersive X-ray spectrometry (EDXS). This glass shows the sole surface crystallization of four different yttrium silicates of the composition Y2Si2O7 (YS). The almost simultaneous but independent nucleation of α-, ß-, δ-, and ε-YS at the surface is followed by growth into the bulk, where ε-YS quickly dominates a first crystallized layer. An accumulation of Mg at the growth front probably triggers a secondary nucleation of ß-YS, which forms a thin compact layer before fragmenting into a highly oriented layer of fine grained crystals occupying the remaining bulk. The residual glass between the YS growth structures allows the crystallization of indialite, yttrium stabilized ZrO2 (Y-ZrO2) and very probably µ-cordierite during cooling. Hence, this glass basically shows the inverted order of crystallization observed in other magnesium yttrium alumosilicate glasses containing less Y2O3. An epitaxial relationship between Y-ZrO2 and ε-YS is proven and multiple twinning relationships occur in the YS phases.

Experimental evidence concerning the significant information depth of electron backscatter diffraction (EBSD).

Experiments concerning the information depth of electron backscatter diffraction (EBSD) are performed on samples featuring an amorphous wedge on a crystalline substrate and a crystalline wedge on an amorphous substrate. The effects of the acceleration voltage and exemplary software settings on the ability to measure through an amorphous layer are presented. Changes in the EBSD-signal could be detected through a ≈142nm thick layer of amorphous Si while orientation measurements could be performed through a ≈116nm thick layer when using a voltage of 30kV. The complexity of the information depth significant to a given EBSD-pattern and the multiple parameters influencing it are discussed. It is suggested that a "core information depth" is significant to high quality patterns while a larger "maximum information depth" becomes relevant when the pattern quality decreases or the sample is inhomogeneous within the information volume, i.e. in the form of partially crystalline materials or crystal layers in the nm scale.

Characterizing the residual glass in a MgO/Al2O3/SiO2/ZrO2/Y2O3 glass-ceramic.

The non-isochemical crystallization of glasses leads to glass-ceramics in which the chemical composition of the amorphous matrix differs from that of the parent glass. It is challenging to solely analyse the properties of these residual glassy phases because they frequently contain finely dispersed crystals. In this study, the composition of the residual glass matrix after the crystallization of a glass with the mol% composition 50.6 SiO2 · 20.7 MgO · 20.7 Al2O3 · 5.6 ZrO2 · 2.4 Y2O3 is analysed by scanning transmission electron microscopy (STEM) including energy dispersive X-ray analysis (EDXS). A batch of the residual glass with the determined composition is subsequently melted and selected properties are analysed. Furthermore, the crystallization behaviour of this residual glass is studied by X-ray diffraction, scanning electron microscopy including electron backscatter diffraction and STEM-EDXS analyses. The residual glass shows sole surface crystallization of indialite and multiple yttrium silicates while bulk nucleation does not occur. This is in contrast to the crystallization behaviour of the parent glass, in which a predominant bulk nucleation of spinel and ZrO2 is observed. The crystallization of the residual glass probably leads to different crystalline phases when it is in contact to air, rather than when it is enclosed within the microstructure of the parent glass-ceramics.

Thermal Expansion of Sintered Glass Ceramics in the System BaO-SrO-ZnO-SiO2 and Its Dependence on Particle Size.

The thermal expansion behavior of sintered glass-ceramics containing high concentrations of Ba1-xSrxZn2Si2O7, a phase with very low and highly anisotropic thermal expansion behavior, was investigated. The observed phase has the crystal structure of the high-temperature phase of BaZn2Si2O7, which can be stabilized by the introduction of Sr(2+) into this phase. The high anisotropy leads to microcracking within the volume of the samples, which strongly affects the dilatometric thermal expansion. However, these cracks also have an influence on the nominal thermal expansion of the as-mentioned phase, which decreases if the cracks appear. Below a grain size of approximately 80 µm, the sintered glass-ceramics have almost no cracks and show positive thermal expansion. Hence, coefficients of thermal expansion between -5.6 and 6.5 × 10(-6) K(-1) were measured. In addition to dilatometric studies, the effect of the microstructure on the thermal expansion was also measured using in situ X-ray diffraction at temperatures up to 1000 °C.

The mechanism of deceleration of nucleation and crystal growth by the small addition of transition metals to lithium disilicate glasses.

The addition of small amounts of niobium or tantalum oxide to lithium disilicate glass provokes a drastic decrease of the steady-state nucleation rates and the crystal growth velocities. The viscosity of the residual glassy matrix is considered as a function of the crystallization degree in the course of a non-isothermal crystallization. For simplification, a homogeneous distribution of the added oxides in the glass matrix is assumed. While the viscosity initially decreases, it significantly increases again for higher crystallization degrees hindering crystal growth. However, it was shown that the additives are enriched at the crystal interface. Several possible reasons for the inhibition of nucleation and growth kinetics such as viscosity, interfacial energy crystal/glassy phase, thermodynamic driving force or impingement rate are discussed. Since the crystallization front is blocked by the additives the impingement rate is decreased with increasing additive concentration. Since small concentrations of Nb2O5 and Ta2O5 have a drastic effect on the nucleation, these components should be enriched at the interface crystal/glass. This will only take place, if it leads to a decrease in the interfacial energy. Since this effect alone should result in an increase of the nucleation rate, it must be overcompensated by kinetic effects.

New Family of Materials with Negative Coefficients of Thermal Expansion: The Effect of MgO, CoO, MnO, NiO, or CuO on the Phase Stability and Thermal Expansion of Solid Solution Phases Derived from BaZn2Si2O7.

Recently, a silicate with the composition SrxBa1-xZn2Si2O7 was reported, which exhibits a negative coefficient of thermal expansion. The compound BaZn2Si2O7 shows a highly positive coefficient of thermal expansion up to a temperature of 280 °C and then transfers to a high temperature phase, which exhibits a coefficient of thermal expansion near zero or negative over a limited temperature range up to around 500 °C. This high temperature modification can be stabilized to room temperature if Ba(2+) is replaced by Sr(2+). In the solid solution SrxBa1-xZn2Si2O7, also Zn(2+) can be replaced in a wide concentration range by other cations with the respective valency. In the present study, Zn was partially or completely replaced by Mg, Co, Mn, Ni, or Cu. If the high temperature phase is stable at room temperature, the thermal expansion is negative, and if the partial substitution exceeds a certain concentration threshold, the low temperature phase with the crystal structure of BaZn2Si2O7 and highly positive thermal expansion is formed. The lowest mean coefficients of thermal expansion were measured for the composition Ba0.5Sr0.5Zn1.4Co0.6Si2O7 with a value of -2.9 × 10(-6) K(-1). In general, a lower Zn-concentration leads to a higher anisotropy and a lower mean coefficient of thermal expansion.

Very high or close to zero thermal expansion by the variation of the Sr/Ba ratio in Ba(1-x)Sr(x)Zn2Si2O7- solid solutions.

The compound BaZn2Si2O7 shows a highly positive coefficient of thermal expansion. At a temperature of 280 °C, it transforms to a high temperature phase, which exhibits a coefficient of thermal expansion near zero. The partial replacement of Ba(2+) against Sr(2+) leads to a decrease of the phase transition temperature. If more than 10% of Ba(2+) are replaced by Sr(2+), the high-temperature phase is completely stable at room temperature and consequently, the thermal expansion is near zero or negative. The effect of the Sr(2+)/Ba(2+)-ratio on the phase transition temperature and the thermal expansion behavior is measured using high-temperature X-ray diffraction up to 1000 °C. The Sr(2+)/Ba(2+)-ratio strongly affects the overall thermal expansion as well as the anisotropy. The latter increases with decreasing Sr-concentration. The strong differences in the thermal expansion behavior between phases with the structure of the low-temperature phase and the high-temperature phase of BaZn2Si2O7 can be explained by a comparison of the ZnO4-chains inside these two crystal structures.

Oriented Nucleation of both Ge-Fresnoite and Benitoite/BaGe4O9 during the Surface Crystallisation of Glass Studied by Electron Backscatter Diffraction.

Two glasses of the compositions 2 BaO - TiO2 - 2.75 GeO2 and 2 BaO - TiO2 -3.67 GeO2 (also known as BTG55) are annealed at temperatures from 680 to 970 °C to induce surface crystallization. The resulting samples are analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) including electron backscatter diffraction (EBSD). Ge-Fresnoite (Ba2TiGe2O8, BTG) is observed at the immediate surface of all samples and oriented nucleation is proven in both compositions. After a very fast kinetic selection, the crystal growth of BTG into the bulk occurs via highly oriented dendrites where the c-axes are oriented perpendicular to the surface. The growth of this oriented layer is finally blocked by dendritc BTG originating from bulk nucleation. The secondary phases BaTiGe3O9 (benitoite) and BaGe4O9 are also identified near the surface by XRD and localized by EBSD which additionally indicates orientation preferences for these phases. This behaviour is in contrast with previous reports from the Ba2TiSi2O8 as well as the Sr2TiSi2O8 systems.