5 Werkstofftechnik
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Structure-property correlations in RE-doped fluoride-phosphate glasses sought by NMR, EPR & PL
(2024)
As the development of optimized glass compositions by traditional trial-and-error methods is laborious, expensive, and time consuming, it is desirable to gather fundamental understanding of structure and to develop structure-property relation models, which allow best and faster choices. Particularly, when it comes to optical applications of glasses doped with emissive trivalent rare earth ions (RE), the chemical environmental around the ions will have a direct influence on the radiative/non-radiative emission probabilities. The vibrational environment and the chemical nature of the bonds in the first coordination sphere of the ions can be tailored, to some extent, based on structural information given by magnetic resonance (NMR and EPR) techniques associated to Raman and photophysical characterization. For the past 5 years, one of the interests of my research group at the University of São Paulo, in Brazil, has been the development of high-density fluoride-phosphate glasses as promising UV and X-ray scintillator materials. The targeted glasses offer a lower vibrational energy, less hygroscopic fluoride environment for the RE ions whereas the phosphate network provides improved mechanical and chemical stability than a purely fluoride glass matrix. Different sets of glasses, based on the compositional system (Ba/Sr)F2-M(PO3)3-MF3-(Sc/Y)F3 where M = Al, In, Ga, and the phosphate component is substituted by the fluoride analogue in 10-30 mol%, were investigated, using Sc3+, Y3+, and the Eu3+ and Yb3+ dopants, as structural probes. Overall, results show that the desired RE coordination by F, at a given F/P ratio, is proportional to the atomic mass of M (In> Ga> Al) and that the Ga- and In- based systems differ from the Al- one by near absence of P-O-P network linkages i.e, the network structures are dominated by Ga-O-P or In-O-P linkages as evidenced by 31P MAS-NMR and Raman. These results are nicely corroborated by observation of decreased intensity in the vibronic band of Eu3+ and significant increase in the excited state lifetime values. Radioluminescence studies were carried out for a series of In-based glasses doped with Ce3+ and Tb3+ yielding intense emissions in the blue and green, respectively, compatible to the spectral region of highest sensitivity of radiation sensor detectors. The aim of the presentation is to show how powerful the combination of NMR, EPR, Raman and PLE spectroscopies can be to provide structural information and to present the perspectives for their introduction in the research agenda of Division 5.6 – Glass, which I now lead, at the Federal Institute for Materials Research and Testing (BAM) in Berlin, Germany.
Quantum dots (QDs) are remarkable semiconductor nanoparticles, whose optical properties are strongly size-dependent. Therefore, the real-time monitoring of crystal growth pathway during synthesis gives an excellent opportunity to a smart design of the QDs luminescence. In this work, we present a new approach for monitoring the formation of QDs in aqueous solution up to 90 °C, through in situ luminescence analysis, using CdTe as a model system. This technique allows a detailed examination of the evolution of their light emission. In contrast to in situ absorbance analysis, the in situ luminescence measurements in reflection geometry are particularly advantageous once they are not hindered by the concentration increase of the colloidal suspension. The synthesized particles were additionally characterized using X-ray diffraction analysis, transition electron microscopy, UV-Vis absorption and infrared spectroscopy. The infrared spectra showed that 3-mercaptopropionic acid (MPA)-based thiols are covalently bound on the surface of QDs and microscopy revealed the formation of CdS. Setting a total of 3 h of reaction time, for instance, the QDs synthesized at 70, 80 and 90 °C exhibit emission maxima centered at 550, 600 and 655 nm. The in situ monitoring approach opens doors for a more precise achievement of the desired emission wavelength of QDs.
The glass system (50NaPO3–20BaF2–10CaF2–20GdF3)-xTbCl3 with x = 0.3, 1, 3, 5, and 10 wt % was investigated. We successfully produced transparent glass ceramic (GC) scintillators with x = 1 through a melt-quenching process followed by thermal treatment. The luminescence and crystallization characteristics of these materials were thoroughly examined using various analytical methods. The nanocrystallization of Tb3+-doped Na5Gd9F32 within the doped fluoride-phosphate glasses resulted in enhanced photoluminescence (PL) and radioluminescence (RL) of the Tb3+ ions. The GC exhibited an internal PL quantum yield of 33 % and the integrated RL intensity across the UV-visible range was 36 % of that reported for the commercial BGO powder scintillator. This research showcases that Tb-doped fluoridephosphate GCs containing nanocrystalline Na5Gd9F32 have the potential to serve as efficient scintillators while having lower melting temperature compared to traditional silicate and germanate glasses.
Upconverting nanoparticles are essential in modern photonics due to their ability to convert infrared light to visible light. Despite their significance, they exhibit limited brightness, a key drawback that can be addressed by combining them with plasmonic nanoparticles. Plasmon-enhanced upconversion has been widely demonstrated in dry environments, where upconverting nanoparticles are immobilized, but constitutes a challenge in liquid media where Brownian motion competes against immobilization.
This study employs optical tweezers for the three-dimensional manipulation of an individual upconverting nanoparticle, enabling the exploration of plasmon-enhanced upconversion luminescence in water. Contrary to expectation, experiments reveal a long-range (micrometer scale) and moderate (20%) enhancement in upconversion luminescence due to the plasmonic resonances of gold nanostructures. Comparison between experiments and numerical simulations evidences the key role of Brownian motion. It is demonstrated how the three-dimensional Brownian fluctuations of the upconverting nanoparticle lead to an “average effect” that explains the magnitude and spatial extension of luminescence enhancement.
The manufacture of sintered glasses and glass-ceramics, glass matrix composites, and glass-bounded ceramics or pastes is often affected by un-expected gas bubble formation also named foaming. Against this background, in this presentation the main aspects and possible reasons of foaming are shown for completely different glass powders: a barium silicate glass powders used as SOFC sealants, and bioactive glass powders using different powder milling procedures.
Sintering and foaming were measured by means of heating microscopy backed up by XRD, differential thermal analysis (DTA), vacuum hot extraction (VHE), optical and electron microscopy, and infrared spectroscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS).
Different densification was reached followed by significant foaming starting partly immediately, partly at higher temperature. Foaming increased significantly as milling progressed. For moderately milled glass powders, subsequent storage in air could also promote foaming. Although the milling atmosphere significantly affects the foaming of uniaxially pressed powder compacts sintered in air.
VHE studies show that foaming is driven by carbon gases and carbonates were detected by Infrared spectroscopy to provide the major foaming source. Carbonates could be detected even after heating to 750 °C, which hints on a thermally very stable species or mechanical trapping or encapsulating of CO2. Otherwise, dark gray compact colors for milling in isopropanol indicate the presence of residual carbon as well. Its significant contribution to foaming, however, could not be proved and might be limited by the diffusivity of oxygen needed for carbon oxidation to carbon gas.
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 at the Institute of Physics of Rennes 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.
Bislang wird das Phänomen der orientierten Oberflächenkristallisation kontrovers diskutiert und entsprechende Studien beschränken sich auf nur wenige Gläser. Für Silikatgläser haben wir eine gute Korrelation zwischen der berechneten Oberflächenenergie von Kristallflächen und der orientierten Oberflächenkeimbildung gefunden. Die Oberflächenenergien wurden unter der Annahme abgeschätzt, dass die Kristalloberflächen bei der Keimbildung den Kristallebenen mit minimaler Energie entsprechen, denen ein Riss beim Bruch folgt. Dieses Konzept wurde am Institut für Physik in Rennes erfolgreich bei der Berechnung der Bruchflächenenergien von Gläsern angewandt. Mehrere orientierte Keimbildungsphänomene lassen sich dadurch erklären, dass man annimmt, dass Kristalloberflächen mit hoher Energie dazu neigen, von der Schmelze benetzt zu werden. Dies minimiert die gesamte Grenzflächenenergie des Keims. Darüber hinaus werden wir die Entwicklung der Mikrostruktur beim weiteren Kristallwachstum und ihre Auswirkungen auf die bevorzugte Kristallorientierung diskutieren.
A widespread recovery of waste heat requires a cost‐effective production of thermoelectric generators. Thermoelectric oxides are predestined for use at high temperatures. For manufacturing reasons, a multilayer generator design will be easily scalable and cost‐effective. To evaluate the potential of ceramic multilayer technology for that purpose, a multilayer of the promising thermoelectric oxides calcium cobaltite (Ca3Co4O9), calcium manganate (CMO, CaMnO3), and glass–ceramic insulation layers is fabricated. Cracks and reaction layers at the interfaces are observed in the microstructure. The compositions of these reaction layers are identified by energy‐dispersive X‐ray spectroscopy and X‐ray diffraction. Mechanical and thermal properties of all layers are compiled from literature or determined by purposeful sample preparation and testing. Based on this data set, the internal stresses in the multilayer after co‐firing are calculated numerically. It is shown that tensile stresses in the range of 50 MPa occur in the CMO layers. The reaction layers have only a minor influence on the level of these residual stresses. Herein, it is proven that the material system is basically suitable for multilayer generator production, but that the co‐firing process and the layer structure must be adapted to improve densification and reduce the tensile stresses in the CMO.
Processing and cytocompatibility of Cu-doped and undoped fluoride-containing bioactive glasses
(2024)
Sintered or additive-manufactured bioactive glass (BG) scaffolds are highly interesting for bone replacement applications. However, crystallization often limits the high-temperature processability of bioactive glasses (BGs). Thus, the BG composition must combine high bioactivity and processability. In this study, three BGs with nominal molar (%) compositions 54.6SiO2-1.7P2O3-22.1CaO-6.0Na2O-7.9K2O-7.7MgO (13–93), 44.8SiO2-2.5P2O3-36.5CaO-6.6Na2O-6.6K2O-3.0CaF2 (F3) and 44.8SiO2-2.5P2O3-35.5CaO-6.6Na2O-6.6K2O-3.0CaF2-1.0CuO (F3–Cu) were investigated. The dissolution and ion release kinetics were investigated on milled glass powder and crystallized particles (500–600 μm). All glasses showed the precipitation of hydroxyapatite (HAp) crystals after 7 days of immersion in simulated body fluid. No significant differences in ion release from glass and crystalline samples were detected. The influence of surface roughness on cytocompatibility and growth of preosteoblast cells (MC3T3-E1) was investigated on sintered and polished BG pellets. Results showed that sintered BG pellets were cytocompatible, and cells were seen to be well attached and spread on the surface after 5 days of incubation. The results showed an inverse relation of cell viability with the surface roughness of pellets, and cells were seen to attach and spread along the direction of scratches.
This study investigates the sintering and crystallization behavior and kinetic of the bioactive glass (BG) 13–93 with nominal composition (in mol%): 54.6 SiO2 - 1.7 P2O3 - 22.1 CaO - 6.0 Na2O - 7.9 K2O - 7.7 MgO. Sintering and crystallization were investigated non-isothermally for various particle size fractions smaller than 315 μm as well as for bulk samples. Densification was not hindered by the presence of crystalline phases across all particle size fractions. Afterwards, wollastonite was found as the dominant crystal phase at higher temperature which resorb primary surface precipitation-like quartz crystallites. The growth direction shifts into volume when the sample surface is nearly covered. The crystal growth rate of wollastonite was calculated from the crystalline surface layer thickness measured during heating. The findings of this study are relevant for the high temperature processing of BG 13–93.