Topology and electronic structure of onion-like carbon and graphite/diamond nanocomposites

Annealing of nanodiamond at moderate temperature makes it possible to produce structures being intermediate in the carbon transformation from sp3 - to sp2-state (graphite/diamond nanocomposites) and onion-like carbon (OLC). Electron microscopy shows such structures involve cage shells with spacing close to graphite. X-ray emission spectroscopy has been applied to examine the electronic structure of OLC and graphite/diamond nanocomposites. The CKα-spectra of OLC produced in the temperature range of 1600-1900 K were found to be markedly different from the spectrum of particles formed at 2140 K and characterized by better ordering of graphitic shells. The latter spectrum was shown to be very Similar to the CKα- spectrum of polycrystalline graphite, while the former ones exhibited a significant increase of high-energy maximum that might be caused by the holed defect structure of graphitic networks forming at the intermediate annealing temperature. To interpret experimental spectra, the quantum-chemical semiempirical AM1 calculation of icosahedral C%40 cage and that with holed defects was carried out. The lack of at least 22% atoms in an internal carbon cage was found to be essential to provide an increase of density of high-energy electronic states similar to that observed in the spectrum of OLC produced at 1900 K

X-ray emission studies of the valence band of nanodiamonds annealed at different temperatures

X-ray emission spectroscopy has been applied to examine the electronic structure of onion-like carbon (OLC) generated by the annealing treatment of nanodiamonds (ND). The C Kα spectra of OLC produced in the temperature range of 1600-1900 K were found to be markedly different from the spectrum of particles formed at 2140 K and to be characterized by better ordering of graphitic shells. The latter spectrum was shown to be very similar to the C Kα of polycrystalline graphite, while the former ones exhibited a significant increase of the high-energy maximum that might be caused by the defect structure of graphitic networks forming at the intermediate temperatures. The experimental spectra were compared with the theoretical spectra from quantum-chemical semiempirical AM1 calculation of several models: a fullerene molecule, C240, having icosahedral structure, a C240 molecule incorporating a greater number of nonhexagonal rings, and a holed structure formed by removing pentagons from the icosahedral molecule. The density of high-energy electronic states in the valence band of the graphitic cage was found to be practically invariant to a change in ring statistics but to significantly increase because of localization of electrons on the zigzag sites of a hole boundary

Topology and electronic structure of onion-like carbon and graphite/diamond nanocomposites

Annealing of nanodiamond at moderate temperature makes it possible to produce structures being intermediate in the carbon transformation from sp3 - to sp2-state (graphite/diamond nanocomposites) and onion-like carbon (OLC). Electron microscopy shows such structures involve cage shells with spacing close to graphite. X-ray emission spectroscopy has been applied to examine the electronic structure of OLC and graphite/diamond nanocomposites. The CKα-spectra of OLC produced in the temperature range of 1600-1900 K were found to be markedly different from the spectrum of particles formed at 2140 K and characterized by better ordering of graphitic shells. The latter spectrum was shown to be very Similar to the CKα- spectrum of polycrystalline graphite, while the former ones exhibited a significant increase of high-energy maximum that might be caused by the holed defect structure of graphitic networks forming at the intermediate annealing temperature. To interpret experimental spectra, the quantum-chemical semiempirical AM1 calculation of icosahedral C%40 cage and that with holed defects was carried out. The lack of at least 22% atoms in an internal carbon cage was found to be essential to provide an increase of density of high-energy electronic states similar to that observed in the spectrum of OLC produced at 1900 K

X-ray emission studies of the valence band of nanodiamonds annealed at different temperatures

X-ray emission spectroscopy has been applied to examine the electronic structure of onion-like carbon (OLC) generated by the annealing treatment of nanodiamonds (ND). The C Kα spectra of OLC produced in the temperature range of 1600-1900 K were found to be markedly different from the spectrum of particles formed at 2140 K and to be characterized by better ordering of graphitic shells. The latter spectrum was shown to be very similar to the C Kα of polycrystalline graphite, while the former ones exhibited a significant increase of the high-energy maximum that might be caused by the defect structure of graphitic networks forming at the intermediate temperatures. The experimental spectra were compared with the theoretical spectra from quantum-chemical semiempirical AM1 calculation of several models: a fullerene molecule, C240, having icosahedral structure, a C240 molecule incorporating a greater number of nonhexagonal rings, and a holed structure formed by removing pentagons from the icosahedral molecule. The density of high-energy electronic states in the valence band of the graphitic cage was found to be practically invariant to a change in ring statistics but to significantly increase because of localization of electrons on the zigzag sites of a hole boundary

Offshore permafrost and gas hydrate stability zone on the shelf of East Siberian Seas

Dynamics of the submarine permafrost regime, including distribution, thickness, and temporal evolution, was modeled for the Laptev and East Siberian Sea shelf zones. This work included simulation of the permafrost-related gas hydrate stability zone (GHSZ). Simulations were compared with field observations. Model sensitivity runs were performed using different boundary conditions, including a variety of geological conditions as well as two distinct geothermal heat flows (45 and 70 mW/m2). The heat flows used are typical for the coastal lowlands of the Laptev Sea and East Siberian Sea. Use of two different geological deposits, that is, unconsolidated Cainozoic strata and solid bedrock, resulted in the significantly different magnitudes of permafrost thickness, a result of their different physical and thermal properties. Both parameters, the thickness of the submarine permafrost on the shelf and the related development of the GHSZ, were simulated for the last four glacial-eustatic cycles (400,000 years). The results show that the most recently formed permafrost is continuous to the 60-m isobath; at the greater depths of the outer part of the shelf it changes to discontinuous and “patchy” permafrost. However, model results suggest that the entire Arctic shelf is underlain by relic permafrost in a state stable enough for gas hydrates. Permafrost, as well as the GHSZ, is currently storing probable significant greenhouse gas sources, especially methane that has formed by the decomposition of gas hydrates at greater depth. During climate cooling and associated marine regression, permafrost aggradation takes place due to the low temperatures and the direct exposure of the shelf to the atmosphere. Permafrost degradation takes place during climate warming and marine transgression. However, the temperature of transgressing seawater in contact with the former terrestrial permafrost landscape remains below zero, ranging from −0.5 to −1.8°C, meaning permafrost degradation does not immediately occur. The submerged permafrost degrades slowly, undergoing a transformation in form from ice bonded terrestrial permafrost to ice bearing submarine permafrost that does not possess a temperature gradient. Finally the thickness of ice bearing permafrost decreases from its lower boundary due to the geothermal heat flow. The modeling indicated several other features. There exists a time lag between extreme states in climatic forcing and associated extreme states of permafrost thickness. For example, permafrost continued to degrade for up to 10,000 years following a temperature decline had begun after a climate optimum. Another result showed that the dynamic of permafrost thickness and the variation of the GHSZ are similar but not identical. For example, it can be shown that in recent time permafrost degradation has taken place at the outer part of the shelf whereas the GHSZ is stable or even thickening