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Eingeladener Vortrag
- nein (26)
Up to now, the mechanisms of surface nucleation and surface-induced texture formation are far from being understood. Corresponding phenomena are discussed hypothetically or even controversial, and related studies are restricted to very few glasses. In this talk the state of the art on mechanisms of surface nucleation are summarized. On one hand, mechanical damaged surfaces show high nucleation activity, at which the nucleation occurs at convex tips and edges preferentially. On the other hand, solid foreign particles are dominant nucleation sites at low damaged surfaces. They enable nucleation at temperatures even far above Tg. The nucleation activity of the particles is substantially controlled by their thermal and chemical durability. But no systematic studies on initially oriented crystal growth or nucleation from defined active nucleation sites have been pursued, so far. Therefore, the main objective of a just started project is to advance the basic understanding of the mechanisms of surface-induced microstructure formation in glass ceramics. We shall answer the question whether preferred orientation of surface crystals is the result of oriented nucleation or caused by other orientation selection mechanisms acting during early crystal growth. In both cases, crystal orientation may be caused by the orientation of the glass surface itself or the anisotropy and orientation of active surface nucleation defects. As a first attempt we focused on possible reorientation of separately growing surface crystals during early crystal growth. First results show clear evidence that separately growing crystals can reorient themselves as they are going to impinge each other.
Up to now, oriented surface crystallization phenomena are discussed controversially, and related studies are restricted to few glasses. For silicate glasses we found a good correlation between the calculated surface energy of crystal faces and oriented surface nucleation. Surface energies were estimated assuming that crystal surfaces resemble minimum energy crack paths along the given crystal plane. This concept was successfully applied by Rouxel in calculating fracture surface energies of glasses. Several oriented nucleation phenomena can be herby explained assuming that high energy crystal surfaces tend to be wetted by the melt. This would minimize the total interfacial energy of the nucleus. Furthermore, we will discuss the evolution of the microstructure and its effect on the preferred crystal orientation.
Up to now, the mechanisms of surface nucleation and surface-induced texture formation are far from being understood. Corresponding phenomena are discussed hypothetically or even controversial, and related studies are restricted to very few glasses. As a main drawback, the vast majority of previous work on oriented growth of surface crystals do not consider the possible effects of glass surface treatments (like polishing defects, adhered particles and cracks, …) or ambient annealing conditions (vacuum or atmospheric pressure) which both can influence crystal nucleation and growth. Moreover, very few observations of crystal orientation related to surface crystallization were focused on separately growing crystals. In conclusion, up to now, no systematic studies on initially oriented crystal growth or nucleation from defined active nucleation sites have been pursued.
Therefore, the main objective of the proposed project is to gain a basic understanding of the mechanisms of surface-induced microstructure formation in glass ceramics. We shall answer the question whether preferred orientation of surface crystals is the result of oriented nucleation or caused by other orientation selection mechanisms acting during early crystal growth. In both cases, crystal orientation may be caused by the orientation of the glass surface itself or the anisotropy and orientation of active surface nucleation defects.
New techniques of experimental characterization of surface-crystallized glasses shall be applied to find answers to the questions posed above. Based on a controlled preparation and annealing of the glass sample surfaces, that includes the defined creation of active nucleation defects, and followed by the microstructural characterization especially during the very early growth stages of separated surface crystals, the orientation relations between defect and initiated surface crystal will be analyzed. In order to gain new insights, a couple of entirely new microstructure diagnostics techniques, including chemically contrasted XRM, laser-based sample preparation for XRM, and 3D electron backscatter diffraction shall be developed or applied.
This way, using X-ray microscopy as a pivotal technique for the non-destructive 3D characterization of relatively large samples at superior spatial resolution (but also complemented by other microstructure diagnostics techniques, e.g. TEM elemental mappings at cross-sectioned samples) unprecedented insights into the microstructure evolution upon surface crystallization of model glasses will be gained.
Up to now, the mechanisms of surface nucleation and surface-induced texture formation are far from being understood. Corresponding phenomena are discussed hypothetically or even controversial, and related studies are restricted to very few glasses. As a main drawback, the vast majority of previous work on oriented growth of surface crystals do not consider the possible effects of glass surface treatments (like polishing defects, adhered particles and cracks, …) or ambient annealing conditions (vacuum or atmospheric pressure) which both can influence crystal nucleation and growth. Moreover, very few observations of crystal orientation related to surface crystallization were focused on separately growing crystals. In conclusion, up to now, no systematic studies on initially oriented crystal growth or nucleation from defined active nucleation sites have been pursued.
Therefore, the main objective of the proposed project is to gain a basic understanding of the mechanisms of surface-induced microstructure formation in glass ceramics. We shall answer the question whether preferred orientation of surface crystals is the result of oriented nucleation or caused by other orientation selection mechanisms acting during early crystal growth. In both cases, crystal orientation may be caused by the orientation of the glass surface itself or the anisotropy and orientation of active surface nucleation defects.
New techniques of experimental characterization of surface-crystallized glasses shall be applied to find answers to the questions posed above. Based on a controlled preparation and annealing of the glass sample surfaces, that includes the defined creation of active nucleation defects, and followed by the microstructural characterization especially during the very early growth stages of separated surface crystals, the orientation relations between defect and initiated surface crystal will be analyzed. In order to gain new insights, a couple of entirely new microstructure diagnostics techniques, including chemically contrasted XRM, laser-based sample preparation for XRM, and 3D electron backscatter diffraction shall be developed or applied.
This way, using X-ray microscopy as a pivotal technique for the non-destructive 3D characterization of relatively large samples at superior spatial resolution (but also complemented by other microstructure diagnostics techniques, e.g. TEM elemental mappings at cross-sectioned samples) unprecedented insights into the microstructure evolution upon surface crystallization of model glasses will be gained.
The effect of elastic stress and relaxation on crystal nucleation in lithium disilicate glass
(2004)
In the framework of a general theoretical approach recently developed, the effect of elastic stresses on the rate of nucleation of crystallites of critical sizes in the process of crystallization of lithium disilicate glasses is studied. Hereby both the evolution of elastic stresses due to changes in the specific volume of the crystallizing system (i.e., differences in the densities of the melt and the crystal) and their relaxation connected with viscous flow are taken into consideration. If the classical theory of nucleation is employed for the determination of the nucleation rates (modified by taking into account elastic stresses), elastic stresses may lead, for the system under consideration, to a decrease of the nucleation rate by up to two orders of magnitude. As shown, the theory allows an at least qualitatively correct incorporation of the effect of elastic stresses and stress relaxation into the description of nucleation phenomena in glass-forming melts.
To understand the impact of dissolved water on structure and properties, four boron-rich glasses of molar compositions 15-x Na2O x CaO 15 SiO2 70 B2O3 (with x=0, 7.5, 10) and 10 Na2O 15 SiO2 75 B2O3 were prepared and subsequently hydrated (up to 8 wt% H2O). Density measurements show a non-linear trend upon hydration implying large structural changes in particular at water contents<2 wt%. Near-infrared spectroscopy shows hydroxyl groups are the dominant species in all glasses upon the entire range of water content. Molecular H2O is detectable only at total water contents>2 wt%. 11B MAS NMR spectra show that the abundance of BO4 species is mainly controlled by ratio of (Na2O+CaO)/B2O3 while incorporation of water plays a minor role.
Compared to borate glasses, the efficiency of formation of BO4 tetrahedra is favored by crosslinking of the network by SiO4-units. The glass transition temperatures, determined by differential thermal analysis, decreases continuously with water content due to breakage of B-O-B bonds by hydrolysis. However, compared to Silicates and aluminosilicates, the effect of dissolved water is less pronounced which can be explained by weaker B-O-B bonds in comparison to Si-O-Si bonds.
Crack growth velocity in alkali silicate glasses was measured in vacuum across 10 orders of magnitude with double cantilever beam technique. Measured and literature crack growth data were compared with calculated intrinsic fracture toughness data obtained from Young´s moduli and the theoretical fracture surface energy estimated from chemical bond energies. Data analysis reveals significant deviations from this intrinsic brittle fracture behavior. These deviations do not follow simple compositional trends. Two opposing processes may explain this finding: a decrease in the apparent fracture surface energy due to stress-induced chemical changes at the crack tip and its increase due to energy dissipation during fracture.
The process of viscous flow sintering is a phenomenon that is closely linked to the surface properties of the glass particles. In this work, we studied the extreme case of acid-leaching of soda-lime-silicate glass beads of two different particle size distributions and its effects on non-isothermal viscous sintering of powder compacts. Depth profiling of the chemical composition after leaching revealed a near-surface layer depleted in alkali and alkaline earth ions, associated with concurrent hydration as mass loss was detected by thermogravimetry. Heating microscopy showed that acid treatment of glasses shifted the sinter curves to higher temperatures with increasing leaching time. Modelling of the shrinkage with the cluster model predicted a higher viscosity of the altered surface layer, while analysis of the time scales of mass transport of mobile species (Na+, Ca2+ and H2O) during isochronous sintering revealed that diffusion of Na+ can compensate for concentration gradients before sintering begins. Also, exchanged water species can diffuse out of the altered layer, but the depletion of Ca2+ in the altered surface layer persists during the sinter interval, resulting in a glass with higher viscosity, which causes sintering to slow down.
Boratgläser zeigen im allgeneinen eine niedrige Glasübergangstemperatur, Tg, auf Grund der 3fach Koordination des Bors mit Sauerstoff. Der Zusatz von Alkali- und Erdalkalioxiden zur Glaszusammensetzung führt zunächst zu einem Anstieg von Tg auf Grund des Koordinationswechsels des Bors von der 3fach zur 4fach Koordination, was als Borsäureanomalie bekannt ist. Bei hohen Alkalioxidgehalten werden dann zunehmend Nichtbrückensauerstoffe (NBO) auf Kosten des tetraedrisch koordinierten Bor gebildet, was zur Senkung der Viskosität führt. Im Gegensatz zu diesem bekannten Verhalten der Alkalioxide (R2O) ist wenig über die Wirkung von Wasser in Boratgläsern bekannt. Daher sollen in dieser Arbeit die rheologischen Eigenschaf-ten von wasserreichen Kalk-Natron-Boratgläsern unter spezieller Berücksichtigung der Rolle des Wassers näher betrachtet werden. Zu diesem Zweck wurde Tg in Abhängigkeit des Na2O- und H2O-Gehalts mittels Differentialthermoanalyse (DTA) und Mikropenetrationsviskosimetrie untersucht. Die Ergebnisse zeigen, dass im Gegensatz zu Na2O Wasser in allen untersuchten Glä-sern und H2O-Konzentrationsbereichen (< 8 Gew.%) Tg deutlich verringert. Diese Beobachtung weist darauf hin, dass Wasser primär zur Bildung von NBO führt und kaum zu einem Koordina-tionswechsel des Bors beiträgt.
To understand the influence of water and alkalis on aluminosilicate glasses, three polymerized glasses with varying ratios of Na/K were synthesized [(22. 5-x)Na2O-xK2O-22.5 Al2O3-55 SiO2 with x = 0, 7.5, and 11.25]. Subsequently, these glasses were hydrated (up to 8 wt% H2O) in an internally heated gas pressure vessel. The density of hydrous glasses linearly decreased with water content above 1 wt%, consistent with the partial molar volume of H2O of 12 cm3/mol. Near-infrared spectroscopy revealed that hydroxyl groups are the dominant species at water content of <4 wt%, and molecular water becomes dominating at water content of >5 wt%. The fraction of OH is particularly high in the pure Na-bearing glass compared to the mixed alkali glasses. 27Al magic angle spinning-NMR spectroscopy shows that aluminum is exclusively fourfold coordinated with some variations in the local geometry. It appears that the local structure around Al becomes more ordered with increasing K/Na ratio. The incorporation of H2O reinforces this effect. The differential thermal analysis of hydrous glasses shows a significant mass loss in the range of glass transition already during the first upscan, implying the high mobility of water in the glasses. This observation can be explained by the open structure of the aluminosilicate network and by the low dissociation enthalpy of H2O in the glasses (≈ 8 kJ/mol). The effect of the dissolved H2O on the glass transition temperature is less pronounced than for other aluminosilicate glasses, probably because of the large fraction of Al in the glasses.
In the present study we have investigated whether the effect of water on properties of borate glasses resembles that of alkali oxide. Soda-lime-borate glasses with nominal compositions of x Na2O, 10 CaO, (90-x) B2O3 (x = 5, 15 and 25 mol%) were doped with up to 8 wt.% H2O by processing glass powder + distilled water in platinum capsules in an internally heated gas pressure vessel at 1523 K and 500 MPa. The water content of hydrous glasses was determined by Karl-Fischer titration and near-infrared spectroscopy. The glass transition temperature T-g. was derived from DTA and micropenetration experiments for which the effect of water loss at the surface of the hydrous glasses was studied. Heating glass samples at 10 K min(-1) in the DTA resulted in T-g values which are close to T-12 isokom temperatures confirming the equivalence of enthalpy relaxation and viscous relaxation for borate glasses. For all three glass series it is shown that T-g strongly decreases whereas the liquid fragility strongly increases upon the addition of water. These findings reveal that H2O primarily causes breaking of B-O-B bonds rather than supporting 4-fold coordinated boron as it is well-known for alkali oxides in this concentration range. (C) 2015 Elsevier B.V. All rights reserved.
The structural investigation of hydrated borate glasses provides new insights on the influence of water on boron speciation using spectroscopic methods. In the present study three soda–lime–borate glasses (NCBx with x = 5, 15 and 25 corresponding to xNa2O, 10CaO, 90 - xB2O3 in mol%) were prepared with water content up to 8 wt.%. The water speciation in the glasses was derived by near-infrared (NIR) spectroscopy while boron speciation was investigated by 11B MAS NMR (Magic Angle Spinning Nuclear Magnetic Resonance). For the three glasses effective molar absorption coefficients were determined experimentally for the bands at 5200 cm- 1 and 4600 cm- 1, corresponding to combination modes of H2O molecules and OH-groups, respectively. In contrast to silicate glasses, in which at most ~ 2 wt.% H2O are dissociated to OH-groups, the amount of dissociated H2O may even exceed 5 wt.% in borate glasses. The fraction of tetrahedral to total boron (N4 = BIV / BIV + BIII) is predominantly controlled by the ratio of Na2O + CaO / B2O3, but only weakly affected by the water content of the glasses. When increasing the H2O content from 0 to 8 wt.%, N4 increases from 25% to 26% for NCB5 and from 42% to 47% for NCB25 glasses.