5 Werkstofftechnik
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Characterization of early crystallization stages in surface-crystallized diopside glass-ceramics
(2019)
Structure formation in glass-ceramics by means of surface crystallization is a challenging open question and remains elusive to definite answers. In several glass-ceramic systems, oriented crystal layers have been observed at the immediate surface, including diopside and some fresnoite systems. However, it is still open to debate, whether oriented surface crystallization is the result of oriented nucleation or growth selection effects. In the same vein, there is still discussion whether surface nucleation is governed by surface chemistry effects or by defects serving as active nucleation sites.
In order to help answer these questions, annealing experiments at 850°C have been performed on a MgO·CaO·2SiO2 glass, leading to the crystallization of diopside at the surface. Different annealing durations and surface treatment protocols (i.a. lapping with diamond slurries between 16 µm and 1 µm grain size) have been applied. Particular focus has been put on earliest crystallization stages, with crystal sizes down to about 200 nm. The resultant microstructure has been analyzed by electron backscatter diffraction (EBSD) and two different kinds of textures have been observed, with the a- or b-axis being perpendicular to the sample surface and the c-axis lying in the sample plane. Even at shortest annealing durations, a clear texture was present in the samples. Additionally, selected samples have been investigated with energy-dispersive x-ray spectroscopy in the scanning transmission electron microscope (STEM-EDX). The diopside crystals have been found to exhibit distinguished submicron structure variations and the glass around the crystals was shown to be depleted of Mg.
A heat treated glass that formed crystals under controlled conditions can be a glass ceramic. A proper understanding of crystallization in glassy melts is needed yet still lacking. Involved processes include the mobility of Elements within the glass during heat treatment and the reorganization of atomic bonds during crystallization. This change in coordination number of certain elements is easily observable in bulk glass samples during heat treatment with XAS. Our plan was to monitor these reorganization processes in situ at the immediate surface during heat treatment with PEEM to get time and spatial resolved data.
The effect of structural water on density, elastic constants and microhardness of water-bearing soda-lime-silica glasses of up to 21.5 mol% total water is studied. It is found that the Poisson ratio and the water content are positively correlated, while density and the elastic moduli decrease with increasing water content. Vickers hardness decreases by approximately 27% from the dry to the most hydrous glass. For water fractions <3 mol%, the dependencies are non-linear reflecting the non-linear change in the concentrations of OH and H2O molecules dissolved, whereas for water fractions >3 mol% linear dependencies are found. To distinguish the effect of structural water and environmental water, indentations were performed in toluene, nitrogen gas and air. Timedependent softening was evident for testing dry glasses in humid atmospheres as well as for tests of hydrous glasses in dry atmospheres. This indicates that the response times of dissolved water species are effectively equal in both scenarios.
Up to now, the mechanisms of surface nucleation and surface-induced texture formation are far from being understood. Very few observations of crystal orientation were focused on separately growing surface crystals. In conclusion, no systematic studies on initially oriented crystal growth or nucleation from defined active surface nucleation sites exists. Therefore, the main objective of this just is to advance the basic understanding of the mechanisms of surface-induced microstructure formation in glass ceramics. As a first attempt, we focus on reorientation of separately growing surface crystals during their early growth.
Glass
(2019)
Overview about the key activities of division 5.6 glass and the diversity of the material glass. For the vacuum hot extraction method (VHE-MS) some examples are presented e. g. for the measurement of water content or the determination of diffusion coefficient of hydrogen in glasses. Finally, an outlook is shown on the robot controlled glass screening device which will be available next year.
Glass powders are promising candidates for manufacturing a broad diversity of sintered materials like sintered ¬glass-ceramics, glass matrix composites or glass bonded ceramics with tailored mechanical, thermal, electrical and optical properties and complex shape. Its wide and precise adjustability makes this class of materials a key component for advanced technologies. Processing of glass or composite powders often allow even more flexibility in materials design. At the same time, however, processing can have substantial effects on the glass powder surface and sinterability. Thus, mechanical damage and surface contamination can strongly enhance surface crystallization, which may retard or even fully prevent densification. Whereas sintering and concurrent crystallization have been widely studied, partially as cooperative effort of the TC7 of the ICG, and although glass powder sintering is predominantly applied for glasses of low crystallization tendency, sintering is also limited by gas bubble formation or foaming. The latter phenomenon is much less understood and can occur even for slow crystallizing glass powders. The lecture illustrates possible consequences of glass powder processing on glass sintering, crystallization and foaming.
Glass powders are promising candidates for manufacturing a broad diversity of sintered materials like sintered glass-ceramics, glass matrix composites or glass bonded ceramics with tailored mechanical, thermal, electrical and optical properties and complex shape. Its wide and precise adjustability makes this class of materials a key component for advanced technologies. Processing of glass or composite powders often allow even more flexibility in materials design. At the same time, however, processing can have substantial effects on the glass powder surface and sinterability. Thus, mechanical damage and surface contamination can strongly enhance surface crystallization, which may retard or even fully prevent densification. Whereas sintering and concurrent crystallization have been widely studied, partially as cooperative effort of the TC7 of the ICG, and although glass powder sintering is predominantly applied for glasses of low crystallization tendency, sintering is also limited by gas bubble formation or foaming. The latter phenomenon is much less understood and can occur even for slow crystallizing glass powders. The lecture illustrates possible consequences of glass powder processing on glass sintering, crystallization and foaming.
Physical storage of gaseous hydrogen under high-pressure in glassy micro-containers such as spheres and capillaries is a promising concept for enhancing safety and the volumetric capacity of mobile hydrogen storage systems. As very low permeation through the container wall is required for storage of compressed hydrogen, development of glasses of minimal hydrogen permeability is needed. For this purpose, one has to understand better the dependence of hydrogen permeability on glass structure. The paper points out that minimizing the accessible free volume is as one strategy to minimize hydrogen permeability. Based on previously measured and comprehensive literature data, it is shown that permeation is independently controlled by ionic porosity and network modifier content. Thus, ionic porosity in modified and fully polymerized networks can be decreased equally to the lowest hydrogen permeability among the glasses under study. Applying this concept, a drop of up to 30,000 with respect to the permeation of hydrogen molecules through silica glass is attainable.
We present an easy-to-apply method to predict structural trends in the internal nucleation tendency of oxide glasses. The approach is based on calculated crystal fracture surface energies derived from easily accessible diatomic bond energy and crystal lattice data. The applicability of the method is demonstrated on literature nucleation data for isochemically crystallizing oxide glasses.
Liquid phase sintering of glass bearing silver pastes used in photovoltaics and microelectronics is poorly understood. In particular, the role of different network modifiers acting in the glass component and the question of the most suitable atmospheric oxygen level during sintering are still under considerable debate. To tackle these issues, low-melting and lead-free X2O-ZnO-B2O3 glasses with X = Li, Na, K and Rb (LZB, NZB, KZB and RZB) were prepared. Infrared spectroscopy showed that the glass structure was similar to each other, while an increase of tetrahedrally coordinated boron with increasing field strength of the alkali was evident. In turn, the glass transition temperature (from differential thermal analysis) increased in the order: RZB (449 °C) < KZB (460 °C) < NZB (465 °C) < LZB (472 °C). Powders of each glass were mixed with organics to receive silver-glass-pastes containing 30 vol% glass and these were subjected to heating microscopy in air. Although similar onset temperatures of sintering were recorded for Ag-NZB and Ag-LZB glass pastes, and for Ag-RZB paste and KZB-Ag-paste, respectively, differences in the crystallization behavior and final densification were observed between the former and the latter group. These were translated in terms of differences in silver dissolution and reprecipitation among the two groups. Further, running the experiments in nitrogen gas showed that sintering of all pastes was considerably hampered. The slow-down of the sinter kinetics was found to be in line with the assumed lower oxidation and dissolution of silver ions into the glass-forming liquid.