12 resultados para intermolecular forces

em Aston University Research Archive


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This paper proposes a semantic analysis of the French free-choice indefinite 'n’importe qui'. The semantics of the indefinite is organised as a ternary structure. The (1) abstract meaning underlies all uses of the item and acts as a principle of creative interpretation generation and comprehension. This principle is actualised via (2) discrete contextual features through to (3) contextual interpretations. Thus, the “existential” reading of 'n’importe qui' is derived by a veridical reading of the arbitrary selection of a qualitatively-marked occurrence from the set of human animates. The derivation of contextual readings from the enrichment by contextual cues of an underspecified meaning has a claim to an explanatory model of the semantics of grammatical polysemous items, and is certainly relevant to model-theoretic approaches in as much as formal semantic notions are intricately linked to the contextual interpretation of items. It is not 'n’importe qui' itself, but its contextual interpretations which may be weak or strong, and an homonymous treatment is not possible given the continuity of the quality and free-choice dimensions from one observed reading of n’importe qui to the next.

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A recent method for phase equilibria, the AGAPE method, has been used to predict activity coefficients and excess Gibbs energy for binary mixtures with good accuracy. The theory, based on a generalised London potential (GLP), accounts for intermolecular attractive forces. Unlike existing prediction methods, for example UNIFAC, the AGAPE method uses only information derived from accessible experimental data and molecular information for pure components. Presently, the AGAPE method has some limitations, namely that the mixtures must consist of small, non-polar compounds with no hydrogen bonding, at low moderate pressures and at conditions below the critical conditions of the components. Distinction between vapour-liquid equilibria and gas-liquid solubility is rather arbitrary and it seems reasonable to extend these ideas to solubility. The AGAPE model uses a molecular lattice-based mixing rule. By judicious use of computer programs a methodology was created to examine a body of experimental gas-liquid solubility data for gases such as carbon dioxide, propane, n-butane or sulphur hexafluoride which all have critical temperatures a little above 298 K dissolved in benzene, cyclo-hexane and methanol. Within this methodology the value of the GLP as an ab initio combining rule for such solutes in very dilute solutions in a variety of liquids has been tested. Using the GLP as a mixing rule involves the computation of rotationally averaged interactions between the constituent atoms, and new calculations have had to be made to discover the magnitude of the unlike pair interactions. These numbers have been seen as significant in their own right in the context of the behaviour of infinitely-dilute solutions. A method for extending this treatment to "permanent" gases has also been developed. The findings from the GLP method and from the more general AGAPE approach have been examined in the context of other models for gas-liquid solubility, both "classical" and contemporary, in particular those derived from equations-of-state methods and from reference solvent methods.

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Recently Homer and Percival have postulated that intermolecular van der Waals dispersion forces can be characterized by three mechanisms. The first arises via the mean square reaction field < R1; 2> due to the transient dipole of a particular solute molecule that is considered situated in a cavity surrounded by solvent molecules; this was characterized by an extended Onsager approach. The second stems from the extra cavity mean square reaction field < R2; 2> of the near neighbour solvent molecules. The third originates from square field electric fields E2BI due to a newly characterized effect in which solute atoms are `buffeted' by the peripheral atoms of adjacent solvent molecules. The present work concerns more detailed studies of the buffeting screening, which is governed by sterically controlled parameter (2T - T)2, where and are geometric structural parameters. The original approach is used to characterise the buffeting shifts induced by large solvent molecules and the approach is found to be inadequate. Consequently, improved methods of calculating and are reported. Using the improved approach it is shown that buffeting is dependent on the nature of the solvent as well as the nature of the solute molecule. Detailed investigation of the buffeting component of the van der Waals chemical shifts of selected solutes in a range of solvents containing either H or Cl as peripheral atoms have enabled the determination of a theoretical acceptable value for the classical screening coefficient B for protons. 1H and 13C resonance studies of tetraethylmethane and 1H, 13C and 29Si resonance studies of TMS have been used to support the original contention that three (< R1; 2> , < R2; 2> and E2BI) components of intermolecular van der Waals dispersion fields are required to characterise vdW chemical shifts.

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Developing a means of predicting tool life has been and continues to be a focus of much research effort. A common experience in attempting to replicate such efforts is an inability to achieve the levels of agreement between theory and practice of the original researcher or to extrapolate the work to different materials or cutting conditions to those originally used. This thesis sets out to examine why most equations or models when replicated do not give good agreements. One reason which was found is that researchers in wear prediction, their predictions are limited because they generally fail to properly identify the nature of wear mechanisms operative in their study. Also they fail to identify or recognise factors having a significant influence on wear such as bar diameter. Also in this research the similarities and differences between the two processes of single point turning and drilling are examined through a series of tests. A literature survey was undertaken in wear and wear prediction. As a result it was found that there was a paucity in information and research in the work of drilling as compared to the turning operation. This was extended to the lack of standards that exist for the drilling operation. One reason for this scarcity in information on drilling is due to the complexity of the drilling and the tool geometry of the drill. In the comparative drilling and turning tests performed in this work, the same tool material; HSS, and similar work material was used in order to eliminate the differences which may occur due to this factor. Results of the tests were evaluated and compared for the two operations and SEM photographs were taken for the chips produced. Specific test results were obtained for the cutting temperatures and forces of the tool. It was found that cutting temperature is influenced by various factors like tool geometry and cutting speed, and the temperature itself influenced the tool wear and wear mechanisms that act on the tool. It was found and proven that bar diameter influences the temperature, a factor not considered previously.

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We have studied the kinetics of the phase-separation process of mixtures of colloid and protein in solutions by real-time UV-vis spectroscopy. Complementary small-angle X-ray scattering (SAXS) was employed to determine the structures involved. The colloids used are gold nanoparticles functionalized with protein resistant oligo(ethylene glycol) (OEG) thiol, HS(CH(2))(11)(OCH(2)CH(2))(6)OMe (EG6OMe). After mixing with protein solution above a critical concentration, c*, SAXS measurements show that a scattering maximum appears after a short induction time at q = 0.0322 angstrom(-1) stop, which increases its intensity with time but the peak position does not change with time, protein concentration and salt addition. The peak corresponds to the distance of the nearest neighbor in the aggregates. The upturn of scattering intensities in the low q-range developed with time indicating the formation of aggregates. No Bragg peaks corresponding to the formation of colloidal crystallites could be observed before the clusters dropped out from the solution. The growth kinetics of aggregates is followed in detail by real-time UV-vis spectroscopy, using the flocculation parameter defined as the integral of the absorption in the range of 600-800 nm wavelengths. At low salt addition (<0.5 M), a kinetic crossover from reaction-limited cluster aggregation (RLCA) to diffusion-limited cluster aggregation (DLCA) growth model is observed, and interpreted as being due to the effective repulsive interaction barrier between colloids within the depletion potential. Above 0.5 M NaCl, the surface charge of proteins is screened significantly, and the repulsive potential barrier disappeared, thus the growth kinetics can be described by a DLCA model only.

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DUE TO COPYRIGHT RESTRICTIONS ONLY AVAILABLE FOR CONSULTATION AT ASTON UNIVERSITY LIBRARY AND INFORMATION SERVICES WITH PRIOR ARRANGEMENT

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DUE TO COPYRIGHT RESTRICTIONS ONLY AVAILABLE FOR CONSULTATION AT ASTON UNIVERSITY LIBRARY AND INFORMATION SERVICES WITH PRIOR ARRANGEMENT

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The firm is becoming more and more inclusive in its conception. And yet, marketing studies point to the same overwhelming conclusion that marketing, marketing departments and marketers are being increasingly 'pushed out' - excluded. We argue that where and when inclusion-exclusion intersect in the practice of strategic marketing is important, not least because their powerful boundary-setting and spanning roles have a determinant effect on the places and spaces, within which marketing strategists are (counter-) mobilized. This paper provides new insights relating to the contradictory forces existing around inclusion-exclusion in corporate strategizing. A further aim is to present the position of marketing (non-) influence within this context. The paper provides a unique theoretical contribution by illustrating some of the contradictions, struggles and activities that make the theoretical shift towards strategic inclusivity unstable, partial and by no means inevitable. A further contribution is a linking of this broader strategic debate, with anxieties over the influence of marketing in corporate strategizing. This leads to a discussion of the various ways that marketing research can sooth the anxiety of influence on multiple fronts via: understanding agency and strategic action; shaping marketing curriculum development; and, reconsidering the spatial dimensions of marketing influence. © 2010 Taylor & Francis.

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The effect of friction and interparticle cohesion forces on the gas-solid flow hydrodynamics was discussed. A proposed interparticle cohesion and frictional force terms have been tested in a continuum fully developed flow model to investigate their effect on the general hydrodynamic features of vertical duct flow. It was observed that both terms have direct effect on lowering the material carryover, which implies a reduced bed expansion in freely bubbling column. The parametric analysis shows that cohesion and frictional forces are high when compared to kinetic stress and hence it can play a major role in describing the hydrodynamics features of the flow.

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Cell exclusion is the phenomenon whereby the hematocrit and viscosity of blood decrease in areas of high stress. While this is well known in naturally occurring Poiseuille flow in the human body, it has never previously been shown in Couette flow, which occurs in implantable devices including blood pumps. The high-shear stresses that occur in the gap between the boundaries in Couette flow are known to cause hemolysis in erythrocytes. We propose to mitigate this damage by initiating cell exclusion through the use of a spiral-groove bearing (SGB) that will provide escape routes by which the cells may separate themselves from the plasma and the high stresses in the gap. The force between two bearings (one being the SGB) in Couette flow was measured. Stained erythrocytes, along with silver spheres of similar diameter to erythrocytes, were visualized across a transparent SGB at various gap heights. A reduction in the force across the bearing for human blood, compared with fluids of comparable viscosity, was found. This indicates a reduction in the viscosity of the fluid across the bearing due to a lowered hematocrit because of cell exclusion. The corresponding images clearly show both cells and spheres being excluded from the gap by entering the grooves. This is the first time the phenomenon of cell exclusion has been shown in Couette flow. It not only furthers our understanding of how blood responds to different flows but could also lead to improvements in the future design of medical devices.