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- Acid rock drainage (1)
- Al13 (1)
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- Anion exchange (1)
- Arsenic retention (1)
- Basaluminite (1)
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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.
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.
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,