High temperature stability of maghemite in partially oxidized basalt lava

Mössbauer spectroscopy of basalt lava samples, exhibiting reversible thermal magnetization (J_S-T) curves with Curie temperatures of about 580°C, has revealed considerable amounts of maghemite (γ-Fe₂O₃) in many samples. In view of the expected instability, of maghemite at temperatures above 350°C, this reversibility is rather surprising. Here we report Mössbauer studies on heated lava samples, showing high content of maghemite. The samples were kept at 600°C in oxidizing, reducing, and inactive atmospheres, respectively, for different lengths of time, and then analyzed with Mössbauer spectroscopy at room temperature. The Mössbauer spectra showed that maghemite is stable in the oxidizing atmosphere for at least several hours. In the inactive atmosphere a considerable amount of maghemite still exists after two hours heating. In the reducing atmosphere maghemite had transformed to magnetite after only 30 minutes.     

Theoretical stability,thin film synthesis and transport properties of the Mon +1GaCn MAX phase

The phase stability of Mo_{n +1}GaC_n has been investigated using ab‐initio calculations. The results indicate stability for the Mo₂GaC phase only, with a formation enthalpy of –0.4 meV per atom. Subsequent thin film synthesis of Mo₂GaC was performed through magnetron sputtering from elemental targets onto Al₂O₃ [0001], 6H‐SiC [0001] and MgO [111] substrates within the temperature range of 500 °C and 750 °C. High structural quality films were obtained for synthesis on MgO [111] substrates at 590 ºC. Evaluation of transport properties showed a superconducting behavior with a critical temperature of approximately 7 K, reducing upon the application of an external magnetic field. The results point towards the first superconducting MAX phase in thin film form. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

On the formation of hydrogen peroxide in water microdroplets

Recent reports on the formation of hydrogen peroxide (H₂O₂) in water microdroplets produced via pneumatic spraying or capillary condensation have garnered significant attention. How covalent bonds in water could break under such mild conditions challenges our textbook understanding of physical chemistry and water. While there is no definitive answer, it has been speculated that ultrahigh electric fields at the air–water interface are responsible for this chemical transformation. Here, we report on our comprehensive experimental investigation of H₂O₂ formation in (i) water microdroplets sprayed over a range of liquid flow-rates, (shearing) air flow rates, and air composition, and (ii) water microdroplets condensed on hydrophobic substrates formed via hot water or humidifier under controlled air composition. Specifically, we assessed the contributions of the evaporative concentration and shock waves in sprays and the effects of trace O₃(g) on the H₂O₂ formation. Glovebox experiments revealed that the H₂O₂ formation in water microdroplets was most sensitive to the air–borne ozone (O₃) concentration. In the absence of O₃(g), we could not detect H₂O₂(aq) in sprays or condensates (detection limit ≥250 nM). In contrast, microdroplets exposed to atmospherically relevant O₃(g) concentration (10–100 ppb) formed 2–30 µM H₂O₂(aq), increasing with the gas–liquid surface area, mixing, and contact duration. Thus, the water surface area facilitates the O₃(g) mass transfer, which is followed by the chemical transformation of O₃(aq) into H₂O₂(aq). These findings should also help us understand the implications of this chemistry in natural and applied contexts.

A. Gallo Jr, H. Mishra et al., pinpoint the origins of the spontaneous H₂O₂ formation in water microdroplets formed via spraying or condensation, i.e., without the addition of electrical energy, catalyst, or co-solvent.     

Rates of redox reactions in basaltic melts determined by Mössbauer spectroscopy

Mössbauer spectroscopy has been widely used for determining the ferric/ferrous ratio in amorphous rock samples to reveal the oxygen pressure in the melt. In the present investigation, Mössbauer spectroscopy in conjunction with melting experiments at controlled oxygen pressures was used to determine the rates of redox reactions in basaltic melts at 1300°C. The samples were kept at a fixed oxygen pressure long enough to reach equilibrium at a well established ferric/ferrous ratio. Then, the oxygen fugacity in the furnace was changed abruptly and the samples were kept for different lengths of time, from 15 min, to 4 hrs, at the new condition. At the end of each run the samples were quenched and the ferric/ferrous ratio analyzed by Mössbauer spectroscopy. A geological corollary of our results is that natural volcanic glasses, representing quenched melts, retain and reflect the oxidation state in the melt immediately prior to eruption, and hence the oxygen fugacity in the magma.     

Efficient computation of Lyapunov functions for nonlinear systems by integrating numerical solutions

Nonlinear Dynamics - A strict Lyapunov function for an equilibrium of a dynamical system asserts its asymptotic stability and gives a lower bound on its basin of attraction. For nonlinear systems,...     

The ferric/ferrous ratio in basalt melts at different oxygen pressures

Samples of two types of natural basalt were equilibrated over a range of oxygen pressures at four different temperatures, and then quenched to room temperature. Except at the lowest temperature, where magnetic crystals formed under the most oxidizing conditions, totally amorphous samples were obtained. The Mössbauer spectra of 45 samples of the quenched basaltic melts were measured at room temperature. The relationship obtained between the oxidation state and oxygen fugacity differs to some extent from those relations previously described in the literature, in not yielding a linear relationship between log(farric/ferrous) and log(fo₂). This might indicate a more involved redox process than that described by a simple reaction between oxides and/or the influence of the cation composition in the process of glass formation. An investigation was made of the kinetics of the redox process. For the experimental setup used, redox equilibrium would be reached within three hours. Finally, three naturally quenched basalt glasses were analyzed for comparison; two showed lower oxidation states than previously found in Icelandic rocks.     

Maghemite in basalt studied by Mössbauer spectroscopy in external magnetic field

In the present study, we investigate the feasibility of detecting and determining the presence of maghemite in rock samples, by obtaining Mössbauer spectra in an external magnetic field of 1.6 T at room temperature. The interaction of the external magnetic field and the magnetic moments of the sublattices will induce differential shifts in the peak positions. By this method, we can assign some lower limit of the amount of maghemite in the sample. The results are compared with a model for a mixture of maghemite and stoichiometric magnetite.     

Enhancing control of grid distribution in algebraic grid generation

Three techniques are presented to enhance the control of grid-point distribution for a class of algebraic grid generation methods known as the two-, four- and six-boundary methods. First, multidimensional stretching functions are presented, and a technique is devised to construct them based on the desired distribution of grid points along certain boundaries. Second, a normalization procedure is proposed which allows more effective control over orthogonality of grid lines at boundaries and curvature of grid lines near boundaries. And third, interpolating functions based on tension splines are introduced to control curvature of grid lines in the interior of the spatial domain. In addition to these three techniques, consistency conditions are derived which must be satisfied by all user-specified data employed in the grid generation process to control grid-point distribution. The usefulness of the techniques developed in this study was demonstrated by using them in conjunction with the two- and four-boundary methods to generate several grid systems, including a three-dimensional grid system in the coolant passage of a radial turbine blade with serpentine channels and pin fins.