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31.
A new inelastic structural control algorithm is proposed by incorporating the force analogy method (FAM) with the predictive instantaneous optimal control (PIOC) algorithm. While PIOC is very effective in compensating for the time delay for elastic structures, the FAM is highly efficient in performing the inelastic analysis. Unlike conventional inelastic analysis methods of changing stiffness, the FAM analyzes structures by varying the structural displacement field, and therefore the state transition matrix needs to be computed only once. This greatly simplifies the computation and makes inelastic analysis readily applicable to the PIOC algorithm. The proposed algorithm compensates for the time delay that happens in practical control systems by predicting the inelastic structural response over a period that equals the magnitude of the time delay. A one‐story frame with both strain‐hardening and strain‐softening inelastic characteristics is analyzed using this algorithm. Results show that the proposed control algorithm is feasibile for any inelastic structures. While the control efficiency deteriorates with the increase in magnitude of the time delay, the PIOC maintains acceptable performance within a wide range of time delay magnitudes. Finally, a computer model of a six‐story moment‐resisting steel frame is analyzed to show that PIOC has good control results for real inelastic structures. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   
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The atomic and electronic structure of mineral surfaces affects many environmentally important processes such as adsorption phenomena. They are however rarely considered relevant to dissimilatory bacterial reduction of iron and manganese minerals. In this regard, surface area and thermodynamics are more commonly considered. Here we take a first step towards understanding the nature of the influence of mineral surface structure upon the rate of electron transfer from Shewanella oneidensis strain MR-1 outer membrane proteins to the mineral surface and the subsequent effect upon cell “activity.” Cell accumulation has been used as a proxy for cell activity at three iron oxide single crystal faces; hematite (001), magnetite (111) and magnetite (100). Clear differences in cell accumulation at, and release from the surfaces are observed, with significantly more cells accumulating at hematite (001) compared to either magnetite face whilst relatively more cells are released into the overlying aqueous phase from the two magnetite faces than hematite. Modeling of the electron transfer process to the different mineral surfaces from a decaheme (protoporphyrin rings containing a central hexacoordinate iron atom), outer membrane-bound cytochrome of S. oneidensis has been accomplished by employing both Marcus and ab initio density functional theories. The resultant model of electron transfer to the three oxide faces predicts that over the entire range of expected electron transfer distances the highest electron transfer rates occur at the hematite (001) surface, mirroring the observed cell accumulation data. Electron transfer rates to either of the two magnetite surfaces are slower, with magnetite (111) slower than hematite (001) by approximately two orders of magnitude. A lack of knowledge regarding the structural details of the heme-mineral interface, especially in regards to atomic distances and relative orientations of hemes and surface iron atoms and the conformation of the protein envelope, precludes a more thorough analysis. However, the results of the modeling concur with the empirical observation that mineral surface structure has a clear influence on mineral surface-associated cell activity. Thus surface structure effects must be accounted for in future studies of cell-mineral interactions.  相似文献   
34.
We report the results of coordinated ion microprobe and transmission electron microscope (TEM) studies of presolar graphites from the KE3 separate (1.65-1.72 g/cm3) of the Murchison CM2 meteorite. Isotopic analysis of individual graphites (1-12 μm) with the ion microprobe shows many to have large 18O excesses combined with large silicon isotopic anomalies, indicative of a supernova (SN) origin. Transmission electron microscopy (TEM) of ultramicrotome slices of these SN graphites revealed a high abundance (25-2400 ppm) of internal titanium carbides (TiCs), with a single graphite in some cases containing hundreds of TiCs. Isotopic compositions of individual TiCs by nanoscale resolution secondary ion mass spectrometry (NanoSIMS) confirmed their presolar origin. In addition to TiCs, composite TiC/Fe grains (TiCs with attached iron-nickel subgrains) and solitary kamacite internal grains were found. In the composite grains, the attached iron phase (kamacite [0-24 at. % Ni] or taenite [up to 60 at. % Ni]) was epitaxially grown onto one or more TiC faces. In contrast to the denser Murchison KFC1 graphites, no Zr-Ti-Mo carbides were observed. The average TiC diameters were quite variable among the SN graphites, from 30 to 232 nm, and were generally independent of the host graphite size. TiC grain morphologies ranged from euhedral to anhedral, with the grain surfaces exhibiting variable degrees of corrosion, and sometimes partially amorphous rims (3 to 15 nm thick). Partially amorphous rims of similar thickness were also observed on some solitary kamacite grains. We speculate that the rims on the internal grains are most plausibly the result of atom bombardment caused by drift of grains with respect to the ambient gas, requiring relative outflow speeds ∼100 km/s (i.e., a few percent of the SN mass outflow speed).Energy dispersive X-ray spectrometry (EDXS) of TiCs revealed significant V in solid solution, with an average V/Ti ratio over all TiCs of ∼83% of the solar value of 0.122. Significant variations about the mean V/Ti ratio were also seen among TiCs in the same graphite, likely indicating chemical equilibration with the surrounding gas over a range of temperatures. In general, the diversity in internal TiC properties suggests that TiCs formed first and had substantially diverse histories before incorporation into the graphite, implying some degree of turbulent mixing in the SN outflows.In most graphites, there is a decrease in the number density of TiCs as a function of increasing radial dis- tance, caused by either preferential depletion of TiCs from the gas or an acceleration of graphite growth with decreasing ambient temperature. In several graphites, TiCs showed a trend of larger V/Ti ratios with increasing distance from the graphite center, an indication of progressive equilibration with the surrounding gas before they were sequestered in the graphites. In all but one graphite, no trend was seen in the TiC size vs. distance from the graphite center, implying that appreciable TiC growth had effectively stopped before the graphites formed, or else that graphite growth was rapid compared to TiC growth. Taken together, the chemical variations among internal grains as well as the presence of partially amorphous rims and epitaxial Fe phases on some TiCs clearly indicate that the phase condensation sequence was TiC, followed by the iron phases (only found in some graphites) and finally graphite. Since graphite typically condenses at a higher temperature than iron at low pressures (<10−3 bars) in a gas with C > O and otherwise solar composition, the observed condensation sequence implies a relative iron enrichment in the gas or greater supersaturation of graphite relative to iron.The TEM observations allow inferences to be made about the physical conditions in the gas from which the grains condensed. Given the TiC sizes and abundances, the gas was evidently quite dusty. From the observed TiC size range of ∼20 nm to ∼500 nm (assuming ∼1 yr growth time and T ∼ 1800°K), we infer minimum Ti number densities in the gas to be ∼7 × 104 to ∼2 × 106 atoms/cc, respectively. Although the gas composition is clearly not solar, for scale, these number densities would correspond to a pressure range of ∼0.2 μbar to ∼5.0 μbar in a gas of solar composition. They also correspond to minimum TiC grain number densities of ∼3 × 10−4 to ∼0.2 grains/cc, assuming complete condensation of Ti in TiC. We estimate the maximum ratio of mean TiC grain separation distance in the gas to grain diameter from the Ti number densities as ∼3 × 105 to ∼1 × 106.  相似文献   
35.
In order to understand the adsorption mechanism of metal atoms to semiconducting surfaces, we have studied, as a model system, the vapor phase adsorption of Ag, Au, and Cu on the (001) surface of molybdenite (MoS2) and the subsequent surface diffusion of these adsorbates. Our scanning tunneling microscopy (STM) images show that, depending on the type of metal atom that is adsorbed, islands of a characteristic size (2 nm for Ag, 8 to 10 nm for Cu, two distinct sizes of 2 nm and 8 to 10 nm for Au), shape (well rounded in the lateral extension) and thickness (one monolayer for Ag, 1 to 1.5 nm for Cu) are formed during the initial stages of deposition. Whole islands are observed to surface diffuse without loss of size or shape. Despite the relatively large size of the copper islands on molybdenite, these islands surface diffuse extensively, suggesting that the Cu-S interaction is weak. Surface diffusion is only hindered once individual islands start to coalesce. As copper islands accumulate, the size and shape of the original islands can still be recognized, supporting the conclusion that these characteristics are constant and that monolayer growth occurs by the aggregation of islands across the surface.The strength and the nature of the Ag-S(MoS2) bond were further investigated by using molecular orbital calculations, ultraviolet photoelectron spectroscopy (UPS) and scanning tunneling spectroscopy (STS). By applying quantum mechanical approaches using a two-dimensional periodic molybdenite slab and hexagonal MoS2 clusters of different sizes with metal atoms adsorbed to them, it is possible to calculate the electron transfer between the mineral surface and the metal atom as well as the adsorption energy as a function of surface coverage. In addition, we used the results from the quantum mechanical runs to derive empirical potentials that model the characteristics of the forces within the crystal, within the adsorbed islands, and the metal and mineral surface. The combination of quantum mechanical calculations and empirical force field calculations explain the electronic structure and the highest stability of Ag islands that have seven atoms in diameter, which exactly agrees with the size of experimentally observed islands. UPS results also suggest that a specific new state is formed (approximately 4.5 eV into the valence band) which may describe the Ag-S bond because it does not occur in pure silver or molybdenite.This study shows how the combination of microscopic (STM), spectroscopic (STS, UPS), compositional (X-ray photoelectron spectroscopy, XPS) and molecular modeling (quantum mechanical and empirical) techniques is a useful approach to understand the nature of the metal to sulfide bond. Further insights may be gained concerning the natural association of certain metals with sulfides.  相似文献   
36.
The range of observed chemical compositions of natural terrestrial waters varies greatly especially when compared to the essentially constant global composition of the oceans.The concentrations of the REEs in natural terrestrial waters also exhibit more variation than what was reported in seawater,In terrestrial waters ,pH values span the range from acid up to alkaline,In addition,terrestrial waters can range from very dilute waters through to highly concentrated brines.The REE concentrations and their behavior in natural terrestrial waters reflect these compositional ranges,Chemical weathering of rocks represents the source of the REEs to natural terrestrial waters and ,consequently,the REE signature of rocks can impart their REE signature to associated waters,In addition,Because of the typical low solubilities of the REEs both surface and solution complexation can be important in fractionating REEs in aqueous solution.Both of these processes are important in all natural terrestrial waters,however,their relative importance varies as a function of the overall solution composition,In alkaline waters,for example,Solution complexation of the REEs with carbonate ions appears to control their aqueous distributions whereas in acid waters,the REE signature of the labile fraction of the REEs is readily leached from the rocks.In circumneutral pH waters,both processes appear to be important and their relative significance has not yet been determined.  相似文献   
37.
Tertiary continental flood basalts on Qeqertarssuaq and Nuussuaq in West Greenland contain ~3?km of picrites and variably contaminated tholeiites. The picrites are in the Naujánguit member of the Vaïgat Formation and they have 7–29?wt% MgO, La/Sm?=?0.9–2.1, and 143Nd/144Nd?=?0.51263–0.51307. They appear to have crystallised from high-Mg parental magmas (14.4–16.4?wt% MgO) with isotope and trace element ratios similar to recent Icelandic picrites. Discrete horizons of tholeiites, including the Asûk and?Kûgánguaq, have elevated SiO2 (50–58 wt%), La/Sm?=?3–7, 87Sr/86Sr?=?0.70550–0.71224, and low 143Nd/144Nd?=?0.51234–0.51174. These lavas have low Cu and Ni abundances (typically 10–50?ppm Ni or Cu), and in the case of the Asûk on Qeqertarssuaq, they contain droplets of native iron. The low Cu and Ni contents are attributed to scavenging by magmatic sulphides formed in response to crustal contamination of picritic magmas. Two contamination trends are recognised, one to a sediment end-member with high Th/Nb and Archaean model Nd ages, and the other to a meta-igneous component with high La/Sm, low Th/Nb and Rb/Nb, and Proterozoic source ages. Overall, 206Pb/204Pb varies from 16.47–21.68. Both contamination trends are associated with low Cu and Ni, and high SiO2, and it is argued that the magmatic sulphides were triggered by the increases in silica, rather than simply by the introduction of additional crustal-derived sulphur. Geochemically, the Asûk and Kûgánguaq rocks resemble the most contaminated Nadezhdinsky lavas of the Siberian Trap, which are widely regarded as the source of the Ni and Cu mineralisation in the giant Noril'sk deposits. Mass balance considerations indicate that the parental liquids to the contaminated magmas contained sufficient Ni, Cu, S and platinum group elements to form substantial magmatic sulphide deposits. However, unlike the lavas at Noril'sk, the contaminated (low Cu and Ni) West Greenland basalts are in isolated units with no evidence for a gradual recovery in Ni and Cu abundances with height in the lava column. Comparison with Noril'sk suggests that although significant quantities of metals were scavenged by sulphides in West Greenland, the metal contents of the sulphides may not have been upgraded by continued interaction with subsequent magma batches.  相似文献   
38.
Discussions regarding weathering in cold environments generally centre on mechanical processes and on the freeze–thaw mechanism in particular. Despite the almost ubiquitous assumption of freeze–thaw weathering, unequivocal proof of interstitial rock water actually freezing and thawing is singularly lacking. Equally, many studies have used the crossing of 0 °C, or values close to that, as the basis for determining the number of ‘freeze–thaw events’. In order to assess the weathering regime at a site in northern Canada, temperatures were collected at the surface, 1 cm and 3 cm depth for sets of paving bricks, with exposures both vertical and at 45°, orientated to the four cardinal directions. Temperature data were collected at 1 min intervals for 1 year. These data provide unequivocal proof for the occurrence of the freezing and thawing of water on and within the rock (freeze–thaw events). The freeze event is evidenced by the exotherm associated with the release of latent heat as the water actually freezes. This is thought to be the ?rst record of such events from a ?eld situation. More signi?cantly, it was found that the temperature at which freezing occurred varied signi?cantly through the year and that on occasion the 1 cm depth froze prior to the rock surface. The change in freeze temperature is thought to be due to the chemical weathering of the material (coupled with on‐going salt inputs via the melting of snowfall), which, it is shown, could occur throughout the winter despite air temperatures down to ?30 °C. This ?nding regarding chemical weathering is also considered to be highly signi?cant. A number of thermal stress events were also recorded, suggesting that rock weathering in cold regions is a synergistic combination of various chemical and mechanical weathering mechanisms. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   
39.
The investigation of the occurrence of lead in dated snow and ice from Greenland and Antarctica has played a major role in our understanding of the history of the pollution of the atmosphere of our planet by this metal. Such studies have however proved to be very demanding, mainly because of the extreme purity of polar snow and ice. Reliable measurements can be obtained only if ultra-clean and highly sensitive procedures are used, as pioneered by Clair Patterson. The Greenland data show evidence of large-scale pollution of the atmosphere of the Northern Hemisphere for lead as early as two millennia ago during Greco–Roman times, especially because of mining and smelting activities in southern Spain. It peaked at the end of the 1960s, with lead concentrations in snow about 200 times higher than natural values, before declining during recent times because of the fall in the use of leaded gasoline. Lead pollution in Antarctica was already significant at the end of the 19th century as a consequence of whaling activities, the traffic of coal-powered ships crossing the Cape Horn, and mining activities in South America, South Africa and Australia. After declining because of the opening of the Panama Canal, the great economic depression and World War II, it reached a maximum during the 1980s, with lead concentrations 20 times higher than natural values. Other studies focus on past natural variations of lead in ancient ice dated from the last climatic cycles. To cite this article: C. Boutron et al., C. R. Geoscience 336 (2004).  相似文献   
40.
Global dust trajectories indicate that signi?cant quantities of aeolian‐transported iron oxides originate in contemporary dryland areas. One potential source is the iron‐rich clay coatings that characterize many sand‐sized particles in desert dune?elds. This paper uses laboratory experiments to determine the rate at which these coatings can be removed from dune sands by aeolian abrasion. The coatings impart a red colour to the grains to which previous researchers have assigned variable geomorphological signi?cance. The quantities of iron removed during a 120 hour abrasion experiment are small (99 mg kg?1) and dif?cult to detect by eye; however, high resolution spectroscopy clearly indicates that ferric oxides are released during abrasion and the re?ectance of the particles alters. One of the products of aeolian abrasion is ?ne particles (<10 µm diameter) with the potential for long distance transport. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   
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