TY - JOUR A1 - Simon, Sebastian A1 - Bertmer, M. A1 - Gluth, Gregor T1 - Sol–gel synthesis and characterization of lithium aluminate (L–A–H) and lithium aluminosilicate (L–A–S–H) gels N2 - Hydrous lithium aluminosilicate (L–A–S–H) and lithium aluminate (L–A–H) gels are candidate precursors for glass-ceramics and ceramics with potential advantages over conventional processing routes. However, their structure before calcination remained largely unknown, despite the importance of precursor structure on the properties of the resulting materials. In the present study, it is demonstrated that L–A–S–H and L–A–H gels with Li/Al ≤ 1 can be produced via an organic steric entrapment route, while higher Li/Al ratios lead to crystallization of gibbsite or nordstrandite. The composition and the structure of the gels was studied by thermogravimetric analysis, X-ray diffraction, 27Al and 29Si magic-angle spinning nuclear magnetic resonance, and Raman spectroscopy. Aluminium was found to be almost exclusively in six-fold coordination in both the L–A–H and the L–A–S–H gels. Silicon in the L–A–S–H gels was mainly in Q4 sites and to a lesser extent in Q3 sites (four-fold coordination with no Si–O–Al bonds). The results thus indicate that silica-rich and aluminium-rich domains formed in these gels. KW - Lithium aluminosilicates KW - Raman spectroscopy KW - Sol-gel PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-558756 DO - https://doi.org/10.1111/ijac.14187 SN - 1546-542X VL - 19 IS - 6 SP - 3179 EP - 3190 PB - Wiley AN - OPUS4-55875 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Stoch, P. A1 - Szczerba, Wojciech A1 - Bodnar, W. A1 - Ciecinska, M. A1 - Stoch, A. A1 - Burkel, E. T1 - Structural properties of iron-phosphate glasses: spectroscopic studies and ab initio simulations N2 - Vitrification is the most effective method for the immobilization of hazardous waste by incorporating toxic elements into a glass structure. Iron phosphate glasses are presently being considered as matrices for the storage of radioactive waste, even of those which cannot be vitrified using conventional borosilicate waste glass. In this study, a structural model of 60P2O5–40Fe2O3 glass is proposed. The model is based on the crystal structure of FePO4 which is composed of [FeO4][PO4] tetrahedral rings. The rings are optimized using the DFT method and the obtained theoretical FTIR and Raman spectra are being compared with their experimental counterparts. Moreover, the proposed model is in very good agreement with X-ray absorption fine structure spectroscopy (XANES/EXAFS) and Mössbauer spectroscopy measurements. According to the calculations the Fe3+ is in tetrahedral and five-fold coordination. The maximal predicted load of waste constituents into the glass without rebuilding of the structure is 30 mol%. Below this content, waste constituents balance the charge of [FeO4]- tetrahedra which leads to their strong bonding to the glass resulting in an increase of the chemical durability, transformation and melting temperatures and density. KW - Glass KW - Iron KW - DFT simulations KW - Mössbauer spectroscopy KW - XANES/EXAFS KW - FTIR spectroscopy KW - Raman spectroscopy KW - Coordination PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-317351 DO - https://doi.org/10.1039/c4cp03113j SN - 1463-9076 SN - 1463-9084 VL - 16 IS - 37 SP - 19917 EP - 19927 PB - The Royal Soc. of Chemistry CY - Cambridge AN - OPUS4-31735 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Seuthe, T. A1 - Mermillod-Blondin, A. A1 - Grehn, M. A1 - Bonse, Jörn A1 - Wondraczek, L. A1 - Eberstein, M. T1 - Structural relaxation phenomena in silicate glasses modifed by irradiation with femtosecond laser pulses N2 - Structural relaxation phenomena in binary and multicomponent lithium silicate glasses were studied upon irradiation with femtosecond (fs) laser pulses (800 nm central wavelength, 130 fs pulse duration) and subsequent thermal annealing experiments. Depending on the annealing temperature, micro-Raman spectroscopy analyses evidenced different relaxation behaviours, associated to bridging and non-bridging oxygen structures present in the glass network. The results indicate that the mobility of lithium ions is an important factor during the glass modification with fs-laser pulses. Quantitative phase contrast imaging (spatial light interference microscopy) revealed that these fs-laser induced structural modifications are closely related to local changes in the refractive index of the material. The results establish a promising strategy for tailoring fs-laser sensitivity of glasses through structural mobility. KW - Femtosecond laser KW - Silicate glasses KW - Raman spectroscopy KW - Structural relaxation KW - Refractive index PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-393045 DO - https://doi.org/10.1038/srep43815 SN - 2045-2322 VL - 7 SP - 43815, 1 EP - 43815, 10 PB - Nature Publishing Group CY - London, UK AN - OPUS4-39304 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sarhan, R. M. A1 - Koopman, W. A1 - Schuetz, R. A1 - Schmid, Thomas A1 - Liebig, F. A1 - Koetz, J. A1 - Bargheer, M. T1 - The importance of plasmonic heating for the plasmondriven photodimerization of 4-nitrothiophenol N2 - Metal nanoparticles form potent nanoreactors, driven by the optical generation of energetic electrons and nanoscale heat. The relative influence of these two factors on nanoscale chemistry is strongly debated. This article discusses the temperature dependence of the dimerization of 4-nitrothiophenol (4-NTP) into 4,4′-dimercaptoazobenzene (DMAB) adsorbed on gold nanoflowers by Surface-Enhanced Raman Scattering (SERS). Raman thermometry shows a significant optical heating of the particles. The ratio of the Stokes and the anti-Stokes Raman signal moreover demonstrates that the molecular temperature during the reaction rises beyond the average crystal lattice temperature of the plasmonic particles. The product bands have an even higher temperature than reactant bands, which suggests that the reaction proceeds preferentially at thermal hot spots. In addition, kinetic measurements of the reaction during external heating of the reaction environment yield a considerable rise of the reaction rate with temperature. Despite this significant heating effects, a comparison of SERS spectra recorded after heating the sample by an external heater to spectra recorded after prolonged illumination shows that the reaction is strictly photo-driven. While in both cases the temperature increase is comparable, the dimerization occurs only in the presence of light. Intensity dependent measurements at fixed temperatures confirm this finding. KW - Nanoparticles KW - Plasmonic heating KW - Raman spectroscopy PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-475140 DO - https://doi.org/10.1038/s41598-019-38627-2 SN - 2045-2322 VL - 9 IS - 1 SP - 3060, 1 EP - 8 PB - Nature Publishing Group AN - OPUS4-47514 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -