TY - JOUR A1 - Knelles, J. A1 - Wanner, C. A1 - Schulz, F. A1 - Freund, M. A1 - Kolmangadi, Mohamed Aejaz A1 - Baro, A. A1 - Huber, P. A1 - Schönhals, Andreas A1 - Lachat, S. T1 - Liquid crystalline hydrazones revisited: dipolar interactions vs hydrogen bonding affecting mesomorphic properties N2 - In order to understand the role of dipolar interactions vs. H-bonding, a series of hydrazones were synthesised from 4-alkoxy-, 3,4-dialkoxy- or 3,4,5-trialkoxybenzaldehydes and phenyl, bromo- or nitrophenylhydrazine, respectively. Their mesomorphic properties were investigated by differential scanning calorimetry (DSC), polarising optical microscopy (POM), X-ray diffraction (WAXS, SAXS) and compared with known members. Only those hydrazones derived from 3,4,5-trisalkoxybenzaldehyde and either meta, meta-dinitro- or ortho, para-dinitrophenylhydrazine displayed hexagonal columnar mesophases. All other derivatives were non-mesomorphic, even when H-bonds were present. Dipole moments of the various nitro-substituted hydrazones were experimentally determined by dielectric measurements and supported by theoretical DFT calculations, which indicated that the mesophase formation is mostly governed by strong dipole moment and further enforced by intramolecular H-bonding. KW - Discotic liquid crystals PY - 2021 DO - https://doi.org/10.1080/02678292.2021.1873438 VL - 48 IS - 10 SP - 1382 EP - 1391 PB - Taylor & Francis AN - OPUS4-52409 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wanner, C. A1 - Poethig, R. A1 - Carrero, S. A1 - Fernandez-Martinez, A. A1 - Jäger, Christian A1 - Furrer, G. T1 - Natural occurrence of nanocrystalline Al-hydroxysulfates: Insights on formation, Al solubility control and As retention N2 - Nanocrystalline basaluminite [Al4OH10(SO4)(H2O)3–5] and Aggregation of the e-Keggin polyoxocation [Al12(AlO4)(OH)24(H2O)12]7+, referred to as Al13, have both been described to form in acid mine Drainage environments. Although the chemical composition is quite similar, their crystalline varieties significantly differ, demonstrating that various types of Al-hydroxysulfates can form under similar conditions and that their respective formation is not fully understood yet. Here, we report the occurrence of nanocrystalline precipitates that form naturally in a small alpine catchment in Switzerland where an acidic mountainous stream (pH 4) is neutralized successively after mixing with several neutral tributaries. The stepwise neutralization in conjunction with the large amount of precipitates provide an ideal setting for obtaining new insights into (i) the structure of naturally forming Al-hydroxysulfates, (ii) their formation mechanism, (iii) their role in controlling the solubility of Al, and (iv) their ability to lower the mobility of As. Synchrotron-based high-energy X-ray diffraction and subsequent pair distribution function analyses demonstrate that these precipitates are structurally identical to basaluminite samples obtained from acid mine drainage sites. In contrast, only minor amounts of tetrahedrally coordinated Al, as present in Al13, were identified by nuclear magnetic resonance spectroscopy. The precipitates are further characterized by elevated As concentrations up to 600 lg/g, whereas other heavy metals are at background concentrations only. Given the low As concentrations in the stream from which precipitation occurs (<0.03 mg/L), high As concentrations confirm that basaluminite serves as a highly efficient As sink, which is attributed to its high anion-exchange capacity. Chemical analysis of streamwater samples in combination with geochemical modeling show that precipitation occurs instantaneously upon mixing with neutral streams. Moreover, our data reveal that the precipitation of basaluminite exerts a strong solubility control on dissolved Al concentrations as manifested by the quasi-constant basaluminite ion activity product observed during neutralization from pH 5 to pH 5.9. We hypothesize that in our field system, high fluoride and sulfate concentrations on the order of 100 and 1–2 mg/L, KW - Basaluminite KW - Al13 KW - Acid rock drainage KW - Arsenic retention KW - Aluminum KW - Anion exchange PY - 2018 DO - https://doi.org/10.1016/j.gca.2018.06.031 SN - 0016-7037 SN - 1872-9533 VL - 238 SP - 252 EP - 269 PB - Elsevier Ltd. AN - OPUS4-46164 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Altenkirch, J. A1 - Gibmeier, J. A1 - Kostov, V. A1 - Kromm, Arne A1 - Kannengießer, Thomas A1 - Doyle, S. A1 - Wanner, A. T1 - Time- and temperature-resolved synchrotron X-ray diffraction: observation of phase transformation and strain evolution in novel low temperature transformation weld filler materials N2 - Solid-state phase transformations and the evolution of thermal and elastic strains in novel low temperature transformation (LTT) weld filler materials in the near surface region are monitored in real time by means of an innovative experimental set-up at the PDIFF (powder diffraction) beamline at the synchrotron light source ANKA (Angströmquelle Karlsruhe) at the KIT (Karlsruhe Institute for Technology). The key components of the diffraction set-up are two fast microstrip line detectors, which enables the strain evolution to be followed as a function of time and temperature for a 0.5?s counting time. During controlled heating and cooling cycles, as well as during near welding cycles, the martensite–austenite–martensite phase transitions are analysed. The transformation kinetics are monitored during resistance heating of small chips of the pure LTT alloys and during gas tungsten arc welding of simplified LTT welds using a specially designed welding rig for in-situ studies on the diffraction instruments. Under the mechanically unconstrained condition allowing free thermal expansion and shrinkage, the LTT alloys are found to exhibit decreasing transformation temperatures Ac and MS and increasing phase fraction of retained austenite for increasing Ni content. The strain evolution during welding reveals increased compressive stresses upon welding, which is attributed to the martensite formation upon cooling, which counteracts the thermal contraction strains. Comparison of the transformation temperatures reveals higher values than in the pure LTT alloys, but no variation between the different alloys. On the one hand, this is attributed to preferred grain orientation affecting the diffraction measurements and the determination of the transformation temperatures. On the other hand, it is possible that with the different chemical compositions of the LTT alloys and the mechanical constraints during welding, the evolution of the residual strain and stress may vary and result in counteracting affects with respect to lowered martensite start temperatures. KW - In-situ synchrotron X-ray diffraction KW - Low temperature transformation KW - Welding PY - 2011 DO - https://doi.org/10.1177/0309324711413190 SN - 0309-3247 SN - 2041-3130 VL - 46 IS - 7 SP - 563 EP - 579 PB - Sage CY - London AN - OPUS4-24683 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -