Search

Piston-cylinder assemblies exhibit inhomogeneous pressure distributions and biases compared to the theoretical pressure applied to the hydraulic press because of the thermal and mechanical properties of the assembly components. Whereas these effects can partially be corrected by conventional calibration, systematic quantification of friction values remain very sparse and results vary greatly among previous studies. We performed an experimental study to investigate the behavior of the most common cell assemblies, i.e., talc [Mg3Si4O10(OH)2], NaCl, and BaCO3, during piston-cylinder experiments to estimate the effects of pressure, temperature, run duration, assembly size, and assembly materials on friction values. Our study demonstrates that friction decreases with time and also partially depends on temperature but does not depend on pressure. We determined that friction decreases from 24 to 17% as temperature increases from 900 to 1300 °C when using talc cells, indicating a friction decrease of ~2% per 100 °C increase for 24 h experiments. In contrast, friction becomes independent of time above 1300 °C. Moreover, at a fixed temperature of 900 °C, friction decreases from 29% in 6 h runs to 21% in 48 h runs, corresponding to a decrease of friction of 0.2% per hour. Similar results obtained with NaCl cell assemblies suggest that friction is constant within error, from 8% in 9 h runs to 5% in 24 h runs. At 900 °C, possible steady-state friction values are only reached after at least 48 h, indicating that friction should be considered a variable for shorter experiments. We establish that assembly materials (and their associated thermomechanical properties) influence the friction correction more than the dimensions of the assembly parts. Finally, we show that the use of polytetrafluoroethylene film instead of conventional Pb foil does not modify friction but significantly reduces the force required for sample extraction, thus increasing the lifetime of the carbide core, which in turn enhances experimental reproducibility.

The behavior of nitrogen during magmatic degassing and the potential kinetic fractionation between N and other volatile species (H, C, O, noble gases) are poorly known due to the paucity of N diffusion data in silicate melts. To better constrain N mobility during magmatic processes, we investigated N diffusion in silicate melts under reducing conditions. We developed uniaxial diffusion experiments at 1 atm, 1425 °C, and under nominally anhydrous reducing conditions fO2$\left(f_{\mathrm{O}_{2}}\right.$≤ IW-5.1, where IW is oxygen fugacity, fO2, reported in log units relative to the iron-wüstite buffer), in which N was chemically dissolved in silicate melts as nitride (N3–). Although several experimental designs were tested (platinum, amorphous graphite, and compacted graphite crucibles), only N diffusion experiments at IW-8 in compacted graphite crucibles for simplified basaltic andesite melts were successful. Measured N difusivity (DN) is on the order of 5.3 ± 1.5 × 10–12m2s–1, two orders of magnitude lower than N chemical diffusion in soda-lime silicate melts (Frischat et al. 1978). This difference suggests that nitride difusivity increases with an increasing degree of melt depolymerization. The dependence of N3–diffusion on melt composition is greater than that of Ar. Furthermore, N3–diffusion in basaltic-andesitic melts is significantly slower than that of Ar in similarly polymerized andesitic-tholeiitic melts at magmatic temperatures (1400–1450 °C; Nowak et al. 2004). This implies that N/Ar ratios can be fractionated during reducing magmatic processes, such as during early Earth’s magma ocean stages.

This work reports on the thermal decomposition of muscovite within a granite powder doped with 8.5 wt% ZnO and heated during 10 min to 68 h at 1175 °C, and the implications for the sequestration of Zn, and other heavy metalts in such decomposition products. Samples were characterized using analytical scanning and transmission electron microscopy. After 10 min, muscovite is completely pseudomorphosed by Si-rich glass, spinel structure phases, and minor mullite. Spinel phases incorporate Zn, but their compositions depend on their position within the muscovite pseudomorphs. Al-rich oxides crystallize at the core of the pseudomorphs while Zn-Al spinels are located at the rims. The most Al-rich spinels have compositions close to ?-Al2O3, a metastable transition alumina, with up to 5 wt% MgO, 2 wt% Fe2O3, 4 wt% ZnO, and 9 wt% SiO2. The most Zn-rich spinels show compositions intermediate between Al2O3 and gahnite (ZnAl2O4), with up to 31 wt% ZnO and significant contents of MgO (3 wt%), Fe2O3(5 wt%), and SiO2(10 wt%). After 68 h, stable spinels are gahnite close to the end-member composition with MgO and Fe2O3contents below ca. 5 wt%, and SiO2contents ca. 1 wt%. These results support the existence of a metastable solid solution between ?-Al2O3and gahnite. This experimental work shows that Zn can be incorporated in spinel structures after heating at 1175 °C during short durations and Zn is preferentially incorporated in the muscovite pseudomorphs as opposed to the Qtz-Fds glass. Consequently, the thermal breakdown of phyllosilicates can be a viable process to immobilize heavy metals such as Zn.