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The paper presents the results of investigation of the 0.4C-35Cr-45Ni-Nb alloy, which operated in the cracked hydrocarbon feeds and dilution steam at 1125 °C. The material originated from the pyrolytic furnace coil tubes, of which internal walls were in contact with the aforementioned medium, whereas the external walls were in contact with the flue gases. The examination included metallographic and mechanical tests on the material after service exposure, the results of which were compared with the ones obtained for the as-received non-exposed specimens. The metallographic tests revealed changes in the alloy's structure manifested by formation of significant amount of the carbides due to carburization of the alloy from the steam and cracked hydrocarbon feeds side. The central and external parts of the alloy samples (having no contact with the process medium) underwent substantial degradation but within a relatively narrow zone of the material. The investigations of hydrogen and methane content in the alloy showed a high amount of these gases, resulting from high-temperature corrosion in steam environment. The mechanical tests demonstrated clear shortening of the plastic deformation range of the alloy due to penetration of the gases and formation of the carbides inside the material's structure. A low level of corrosion and no creep mechanism were detected.

Growth of large-area, few-layer graphene has been reported recently through the catalytic decomposition of methane (CH(4)) over a Cu surface at high temperature. In this study, we used ab initio calculations to investigate the minimum energy pathways of successive dehydrogenation reactions of CH(4) over the Cu (111) surface. The geometries and energies of all the reaction intermediates and transition states were identified using the climbing image nudged elastic band method. The activation barriers for CH(4) decomposition over this Cu surface are much lower than those in the gas phase; furthermore, analysis of electron density differences revealed significant degrees of charge transfer between the adsorbates and the Cu atoms along the reaction path; these features reveal the role of Cu as the catalytic material for graphene growth. All the dehydrogenation reactions are endothermic, except for carbon dimer (C(2)) formation, which is, therefore, the most critical step for subsequent graphene growth, in particular, on Cu (111) surface.

A two-dimensional quantum-mechanical vibrational model has been used to calculate the anharmonic OH vibrational frequencies in the layered Mg(OH)(2) (brucite) crystal. The underlying potential energy surface was generated by density functional theory (DFT) calculations. The resulting OH frequencies are upshifted (blueshifted) by about +75 cm(-1) with respect to the gas-phase OH frequency (+120 cm(-1) in experiments; the discrepancy is mainly due to inadequacies in the DFT and pseudopotential models). The Raman-IR split is about 50 cm(-1), both in the calculations and in experiments. We find that the blueshift phenomenon in brucite can qualitatively be explained by a parabolalike "OH frequency versus electric field" correlation curve pertaining to an OH(-) ion exposed to an electric field. We also find that it is primarily the neighbors within the Mg(OH)(2) layer that induce the blueshift while the interlayer interaction gives a smaller (and redshifting) contribution.

The O-H vibrational frequency in crystalline hydroxides is either upshifted or downshifted by its crystalline surroundings. In the LiOH crystal, the experimental gas-to-solid O-H frequency upshift ("blue shift") is approximately +115 cm(-1). Here plane-wave DFT calculations for the isotope-isolated LiOH crystal have been performed and we discuss the origin of the OH frequency upshift, and the nature of the OH group and the interlayer interactions. We find that (1) the vibrational frequency upshift originates from interactions within the LiOH layer; this OH upshift is slightly lessened by the interlayer interactions; (2) the interlayer O-H - - - H-O interaction is largely electrostatic in character (but there is no hydrogen bonding); (3) the gas-to-solid vibrational shift for OH in LiOH(s) and its subsystems qualitatively adheres to a parabola-like "frequency vs electric field strength" correlation curve, which has a maximum for a positive electric field, akin to the correlation curve earlier found in the literature for an isolated OH(-) ion in an electric field.

Anharmonic vibrational frequencies for the Raman-active (A(1g)) and the IR-active (A(2u)) modes have been calculated for the LiOH crystal within a plane-wave density functional theory (DFT) framework. We find that a two-dimensional quantum-mechanical vibrational approach, allowing for anharmonic coupling between symmetric and antisymmetric OH stretching modes, produces OH frequencies--both absolute frequencies and gas-to-solid frequency shifts--in good agreement with experiment. Remaining errors in the absolute frequencies are largely a consequence of the DFT model chosen. A one-dimensional normal-mode following vibrational treatment, on the other hand, fails to reproduce both absolute anharmonic frequencies and gas-to-solid frequency shifts.