5 Werkstofftechnik
Filtern
Dokumenttyp
- Vortrag (47) (entfernen)
Referierte Publikation
- nein (47)
Schlagworte
- Glass (15)
- Sintering (9)
- Crack growth (7)
- DCB (6)
- Glas (5)
- Water speciation (5)
- Crystallization (4)
- Vickers (4)
- Alkali ions (3)
- Foaming (3)
Organisationseinheit der BAM
- 5.6 Glas (47) (entfernen)
Eingeladener Vortrag
- nein (47)
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.
Substitution of lead oxide in low-melting glasses, e.g., for application in silver metallization pastes, is a current research goal. This work is focused on the investigation of silver diffusion in alkali zinc borate glasses (X2O-ZnO-B2O3, X = Li, Na, K, Rb). In addition, the redox state of silver (Ag) and thus the type of diffusing silver species were studied. For this purpose, a metallic silver coating was applied on glass cubes by means of sputtering. Heat treatment of the samples was performed close to the glass transition temperatures at 470 °C for 2 h under air and nitrogen atmosphere. Coating thickness was 1.8 µm after heat treatment, measured by a white light interferometer.
Silver diffusion profiles were measured by means of secondary neutral mass spectrometry. The silver diffusion coefficients are in the range of ~10-14 cm2/s and indicate no significant differences depending on the type of alkali ions in the glass. Dissolved Ag+-ions and [Agm]n+-clusters in the glasses were differentiated using fluorescence spectroscopy.
Precipitated metallic silver particles in the sodium containing glass were observed by means of transmission electron microcopy. Their mean particle diameter was ~6 nm.
Silber-Glas Wechselwirkungen spielen eine wichtige Rolle zum Beispiel in Glas-haltigen Silberpasten, die in der Photovoltaik oder Mikroelektronik verwendet werden. Um ein besseres Verständnis der Vorgänge zu erhalten, werden niedrig-schmelzende, bleifreie X2O ZnO B2O3 Gläser (X = Li, Na, K und Rb, Abk.: LZB, NZB, KZB and RZB) zur Untersuchung der Pasten verwendet.
Raman und Infrarot Spektroskopie zeigen, dass die Glasstruktur weitgehend vergleichbar ist, aber Unterschiede in der Bildung von Pentaboratgruppen in LZB und NZB oder Diboratgruppen in KZB und RZB auftreten. Die Anzahl an vierfach koordinierten Bor-Ionen (N4) sinkt mit zunehmendem Alkaliionenradius. Die Verringerung von N4 führt zu einer niedrigeren Glasübergangstemperatur in der Reihe LZB (472 °C) < NZB (465 °C) < KZB (460 °C) < RZB (449 °C).
Zur Herstellung der Pasten wurde kommerzielles Silber-Pulver mit 30 Vol.-% Glas und Organik gemischt. Das Sinterverhalten der gepressten Pulver wurde mittels Erhitzungsmikrospie untersucht. Der Sinterbeginn der Pasten ist vergleichbar und korrespondiert mit den geringen Unterschieden der Viskosität bei vergleichbarer Partikelgröße der Gläser. In den Ag-KZB- und Ag-RZB-Pasten ist die Schwindung durch die stärker einsetzende Kristallisation im Vergleich zu LZB und NZB verzögert.
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.
Artificial bone replacement by individual customized three-dimensional resorbable bioactive glass has not yet been widely established in the clinical use. This is mainly due to the antagonism of sintering ability and suitable bioactivity. Competitive crystallization often prevents the generation of dense sintered bodies, especially for additive manufactured 3D structures. Previous studies of the fluoride-containing glass F3 have shown its potential to combine both sintering ability and suitable bioactivity. Furthermore, the occurring sintering blockade by surface crystallization of Na2CaSi2O6 was tunable by glass particle size.
In this study the glasses F3, F3-Cu with 1 mol% CuO added at the expense of CaO and the well-known 13-93 were chosen to determine the influence of surface crystallization on 3D printed sinter bodies. For this purpose, grain size fractions in range of smaller 32 µm to 315 µm in fraction size of 6-20 µm were sieved from jaw crushed glass frit as well as glass cubes were cut from casted blocks for all glasses. Sintering behavior of both pressed and printed powder compacts was observed via heating microscopy. Crystallization was determined by DTA and crystallization progress was monitored on fractured sinter bodies and polished cubes via electron and laser scanning microscopy as well as with diffractometry.
Depending on grain size the formation of crystalline support framework along former grain boundaries shows the capability to stabilize fully densified sinter bodies before softening. Beside of this, the generation of complex hierarchic porosity was possible as well.
Um die Langzeitbeständigkeit von Hochtemperatur-Festoxidbrennstoffzellen (SOFC) sicherzustellen, ist das grundlegende Verständnis der viskosen Schließung oder Heilung von Rissen, als Folge wechselnder thermischer oder mechanischer Belastung, in Gläsern und teilkristallinen Materialien ein entscheidender Faktor. In Glas ist die Rissheilung hauptsächlich durch viskoses Fließen bestimmt. In teilkristallinen Schmelzen bewirkt der kristalline Volumenanteil die Erhöhung der effektiven Viskosität. Um die Auswirkungen des kristallinen Volumenanteils auf die Rissheilung zu ergründen, wurden Glasmatrixkomposite mit variierten inerten kristallinen Fülleranteilen, die während der Wärme-behandlung konstant blieben, hergestellt. Verwendet wurde ein kristallisationsträges Natrium-Calcium-Silicatglas und ZrO2 als inerter Füller. Komplexe, reproduzierbare Rissstrukturen wurden durch Vickers-Eindrücke erzeugt und die viskose Rissschließung während isothermer Wärmebehandlungs-schritte mittels Laser-Scanning-Mikroskopie verfolgt. Die Untersuchungen zeigen, dass, verglichen zum füllerfreien Glas, der kristalline Phasenanteil die effektive Viskosität erhöht und dadurch großräumiges Fließen verlangsamt. Dies verzögert das Aufweiten der Risse. Dieser Effekt erschwert die Rissverkürzung und führt oftmals zu großen gerundeten Kavitäten und dadurch zu einer verzögerten Rissschließung. Wird dieses Aufweiten verringert, ist zunächst ein lokales viskoses Fließen der Restglasphase weiterhin gegeben, sodass sich die Risse sogar schneller schließen. Für kristalline Anteile > 27 Vol% bildet sich dann ein stabiles Perkolationsgerüst aus, das die weitere Rissschließung auch lokal unterbindet. Nur innerhalb größerer glasiger Bereiche ist hierbei noch eine Rissschließung zu beobachten. Ein Optimum der Risslängenverkürzung konnte bei 17 Vol% beobachtet werden.
Die Analyse von Bruchflächen wird in der Schadensanalyse meist auf der Basis von Erfahrungswissen vorgenommen, welches aus vorliegenden Untersuchungen, eigenen Vergleichsversuchen und aus der Literatur stammt. Durch Vergleiche mit bereits vorliegenden Bildern werden qualitativ Bruchmechanismen ermittelt. Grundlage sind zumeist zweidimensionale Bilder aus licht- und elekt-ronenoptischen Verfahren. Quantitative Aussagen beziehen sich bislang beispielsweise auf makroskopische Anteile von Bruchmechanismen oder die Ausmessung von Schwingstreifen. In jüngerer Zeit gibt es vermehrt Ansätze, Computer-Algorithmen einzusetzen, die in der Lage sind, unterschiedlich strukturierte Bruchmerkmale zu finden und zu klassifizieren. Im hier vorgestellten IGF-Vorhaben „iFrakto“, IGF Vorhaben Nr.: 21477 N, werden licht- und elektronenoptisch Topographie-Bilder erzeugt und die gewonnenen 3D-Informationen zusammen mit den klassischen 2D-Bildern ausgewertet.
The lecture focuses on the mechanisms of non-desired gas bubble formation and foaming during the sintering of glass powder compacts. It is shown that foaming is driven by carbon gases and that carbonates, encapsulated in micropores or mechaniacally dissolved beneath the glass surface, provide the major foaming source.
Since decades electric contacts based on silver metallization pastes are key components of photovoltaics and advanced microelectronics. For the metallization of commercial Si solar cells, high conductive silver glass pastes are cost effectively applicated by screen printing. Nevertheless, silver pastes are still one of the most crucial and expensive none Si materials in solar cells. Ever shorter time to market as well as increasing demands on reduced Ag consumption and line width require the targeted development of silver-glass-pastes with increased sinter ability and electrical conductivity. As a main difficulty, however, the liquid phase sintering of silver glass pastes is poorly understood so far.
In the present study, the influence of different network modifier in alkali-zinc-borate paste glasses on liquid phase sintering of silver-glass-pastes was investigated. Low melting X2O-ZnO-B2O3 glasses with X = Na, Li and Rb (abbr. LZB, NZB, and RZB) were utilized to prepare silver-glass-composites containing 30 %Vol glass. Shrinkage behavior of the silver-glass-composites compared with that of pure silver and pure glass powder compacts was studied with heating microscopy. The powder compacts were uniaxially pressed and heated at 5 K/min to the glass softening temperature. Glass transformation temperature and viscosity of the glasses were respectively measured with dilatometry and rotational viscometry. The thermal behavior of the pure glasses was analyzed with thermal analysis. Additionally, the contact angle of glass on pure silver foil was determined by means of heating microscopy between room temperature and 830 °C.
Thermal analysis of the alkali-zinc-borate-glasses under study has shown transformation temperatures between 450 °C (RZB), 460 °C (LZB) and 465 °C (NZB). For all glasses crystallization was found to start approximately at about 550 °C. However, different peak areas hint on a different degree of crystallization. Conformingly, the sintering behavior, measured in terms of area shrinkage, significantly differed for the silver-pastes under study. For silver-pastes with NZB or LZB-glass, sintering starts at 464 °C for NZB Ag pastes and at 451 °C for LZB Ag pastes and ends at 597 °C for NZB Ag paste and at 594 °C for LZB Ag paste. The sintering of the RZB Ag paste proceeds between 426 °C and 703 °C. The final densification was retarded possibly due to crystallization or swelling. The low sinter onset at 426 °C seems to correlate with the good wetting behavior of the RZB glass. Thus, the lowest apparent contact angle between the just densified powder compact sintered at a silver substrate was found for this glass. Moreover, microstructure analyses of the various composites indicate differences in silver dissolution and reprecipitation.
Network modifier ions can decisively influence properties and structure of low melting alkali-zinc-borate glasses and thus cause complex effects on the liquid phase sintering of silver-glass metallization pastes. This effect was studied for X2O-ZnO-B2O3 (X = Li, Na, Rb) glasses for silver-glass metallization pastes. Viscosity and the glass transition temperature, Tg, were measured with rotational viscometry and dilatometry. Dried model pastes with 30 vol% LZB, NZB or RZB glass were prepared for sintering studies by means of heating microscopy measuring the silhouette area shrinkage of uniaxially pressed powder compacts during heating at 5 K/min. For comparison, the silhouette area shrinkage of pure glass and silver powder compacts were determined. Glass-silver wetting was investigated during heating of bulk glass cylinders placed on silver substrates. Glass RZB turned out to have the lowest viscosity among the glasses under study. Its glass transformation temperature, Tg, was found at 444 °C and it caused the lowest sintering onset for its glass and paste powder compacts. Slightly increased values of Tg were found for NZB and LZB (468 °C and 466 °C, respectively) and a slightly retarded sintering was found for both paste powder compacts. These results indicate that liquid phase sintering of silver-glass pastes under air atmosphere is mainly influenced by glass viscosity.