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Nowadays, the use of bioactive glasses is established for bone regeneration; however glasses are used mostly as powders, granules or in a paste. Sintered scaffolds are not used clinically, because of the inherent problem of crystallization during the sintering process, resulting in poor mechanical properties and reduced bioactivity. Therefore it was the aim to design new bioactive glasses, which combine improved processing and sintering with bioactivity.
Compared with the well-known Bioglass® 45S5 (SiO2-P2O5-CaO-Na2O) the calcium/alkali oxide ratio was increased, sodium oxide was partially replaced by potassium oxide and up to 8 mol% calcium fluoride were added, in order to stabilize the glass against crystallization.
The sintering behavior of the new glasses was characterized by heating microscopy and compared to that of Bioglass® 45S5. Results show that the new glasses achieve a sintered density of 88-99 % in contrast to only 57-67% for Bioglass® 45S5. In addition, FTIR and XRD analyses show that Bioglass® 45S5 crystallizes during sintering while for the new glasses no crystalline phases were detected. The thermal properties of all glasses were studied by DTA and DSC measurements, and the influence of grain size was characterized. These studies showed an increase of sintering temperature and final porosity with increasing particle size. The structure of sintered compacts during and after sintering was examined using light and electron microscopy (SEM).
Fundamental understanding of crack healing in glassy crystalline materials is very important for solid oxide fuel cell (SOFC) sealants, since cracks caused by sealing or thermal cycling still remain a substantial bottleneck in developing durable SOFC.
Previous studies on soda lime silicate glass [Sin14] showed that crack healing is driven by viscous flow and that healing progress is proportional to time t and inverse viscosity η. This finding would allow to present healing data of a given glass for different temperatures in a master curve healing progress versus t/η. Such master curves would be a helpful tool in understanding crack healing kinetics.
Against this background, crack healing in non-crystallizing sodium calcium silicate (NCS) and sodium borosilicate glasses (NBS) have been studied. Moreover, to evaluate the influence of micro structure in crystallized glass on crack healing process, glass matrix composites (GMC) were prepared from NCS and zirconia as inert ceramic filler material mimicking a partially crystalline micro structure. By this way, the micro structure can be kept constant during crack healing. Cracks were generated by Vickers indention and healed isothermally at different temperatures. Crack healing progress was monitored by optical and electron microscopy. Results show that the above mentioned proportionality actually applies for the studied glasses for which such a master curve could be obtained. In comparison to a non-crystallized glass, the effective viscosity of GMC is increased by the rigid filler content. This effect substantially retards crack broadening during later healing stages, which often ends up in large pores. On the other hand, local viscous crack healing is still possible in larger glassy regions. This behavior seems to be very interesting for crack healing optimized micro structures.
Fundamental understanding of crack healing in glassy crystalline materials is very important for many applications, especially for sealing solid oxide fuel cells (SOFC) since cracks caused by sealing or thermal cycling still remain a substantial bottleneck in developing durable SOFC.
Previous studies on soda lime silicate glass [Sin14] showed that crack healing is driven by viscous flow and that healing progress is proportional to time t and inverse viscosity η. This finding would allow to present healing data of a given glass for different temperatures in a master curve healing progress versus t/η. Such master curves would be a helpful tool in understanding crack healing kinetics.
Against this background, crack healing in non-crystallizing sodium calcium silicate (NCS) and sodium borosilicate glasses (NBS) have been studied. Moreover, to evaluate the influence of micros structure in crystallized glass on crack healing process, glass matrix composites (GMC) where prepared out of NCS and zirconia as inert ceramic filler material mimicking a partially crystalline micro structure. Cracks were generated by Vickers indention and healed isothermally at different temperatures. Crack healing progress was monitored by optical and electron microscopy. Results show that the above mentioned proportionality actually applies for the studied glasses for which such a master curve could be obtained. In comparison to a non-crystallized glass, the effective viscosity of GMC is increased by rigid filler content. This effect substantially retards crack broadening during later healing stages, which often ends up in large pores. On the other hand, local viscous crack healing is still possible in larger glassy regions. This behavior seems to be very interesting for crack healing optimized sealants.
A summery of previous research regarding surface crystallization is given as well as results regarding thecurrent DFG project are presented.
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.
185 cracks were initiated in a soda-lime-silica glass by Vickers indentation and grown under controlled dry nitrogen atmosphere. Direct observation of subcritical crack growth (SCCG) upon indentation was performed using a video camera with an image acquisition rate of 3 ms. The results show that the validity of K(c) relations used to determine the indentation fracture toughness from a single imprint is questionable. It seems that correlation of crack length to stress intensity necessitate the use of statistical significant data of multiple crack events.
Chemical variability is a main strength of glass. Glass powders are therefore 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, even if it may not be obvious at first sight, a key component of advanced technologies. Manufacture and processing of initial glass powders often allow even more flexibility in materials design. At the same time, however, they can cause additional problems. The lecture illustrates possible consequences of glass powder processing upon glass crystallization and sintering as well as chances for targeted utilization. Simple kinetic models describing the effect of particle size distribution, surface crystallization and rigid inclusions on sintering as well effects of different milling and seeding on sinter crystallization are presented.
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.
Dissolved water decisively influences numerous thermally activated relaxation phenomena in glasses like stress relaxation, sub-critical crack growth, internal friction, viscosity, sintering, and crystallization. Thermoanalytical methods can essentially help for better understanding of these phenomena. The lecture introduces the Vacuum Hot Extraction method (VHE) and illustrates its possibilities for measuring water content, degassing and mobility. As another thermoanalytical method, the Dynamic Mechanical Themoanalysis (DMA), allowing to study the effect of dissolved water on the internal friction in glasses, is introduced.