An improved numerical simulator for multiphase flow in porous media

In basin modelling the thermodynamics of a multicomponent multiphase fluid flux are computationally too expensive when derived from an equation of state and the Gibbs equality constraints. In this article we present a novel implicit molar mass formulation technique using binary mixture thermodynamics. The two proposed solution methods, with and without cross derivative terms between components, are based on a preconditioned Newton‐GMRES scheme for each time‐step with analytical computation of the derivatives. These new algorithms reduce significantly the numerical effort for the computation of the molar masses, and we illustrate the behavior of these methods with numerical computations. Copyright © 2004 John Wiley & Sons Ltd.     

Stabilization of valence fluctuations in the cerium solid by the time-dependent collision approach

The collision-generated hybridization which has been found responsible for the on-site mixing of the atomic-likef-state and the band-liked states in mixed valence solids has been studied for the cerium solid. A practical expression which depends on the lattice constant and temperature has been obtained for the collision-generated hybridization. Numerical calculations show that the valence varies continuously with lattice constant and that temperature makes the transition smoother. The collision-generated hybridization is found to be of significant strength in the intermediate valence regime; but over a wide range of the valence near 3.5 it varies rather slowly without preferring a particular valence. Factors which can assist the collision-generated hybridization in stabilizing the mixed valence phase at a particular lattice constant are discussed.     

Crystalline structure of polyamide 12 as revealed by solid‐state 13C NMR and synchrotron WAXS and SAXS

The crystalline structure of polyamide‐12 (PA12) was studied by solid‐state ¹³C nuclear magnetic resonance (NMR) as well as by synchrotron wide‐ and small‐angle X‐ray scattering (WAXS and SAXS). Isotropic and oriented PA12 showed different NMR spectra ascribed to γ‐ and γ′‐crystalline modifications, respectively. On the basis of the position of the first diffraction peak, the isotropic γ‐form and the oriented γ′‐form were shown to be with hexagonal crystalline lattice at room temperature. When heated, the two PA12 polymorphs demonstrated different behaviors. Above 140 °C, the isotropic γ‐PA12 partially transformed into α‐modification. No such transition was observed with the oriented γ′‐PA12 phase even after annealing at temperatures close to melting. A γ′–γ transition was observed here only after isotropization by melting point. Various structural parameters were extracted from the WAXS and SAXS patterns and analyzed as a function of temperature and orientation: the degree of crystallinity, the d‐spacings, the Bragg's long spacings, the average thicknesses of the crystalline (l_c) and amorphous (l_a) phases, and the linear crystallinity x_cl within the lamellar stacks. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3720–3733, 2005     

Solid state NMR characterization of formation of poly(ϵ‐caprolactone)/maghnite nanocomposites by in situ polymerization

Results of multinuclear MAS NMR spectroscopy are reported for poly (ε‐caprolactone)/maghnite nanocomposite formation, with ε‐caprolactone in situ polymerized in the presence of maghnite, a proton exchanged montmorillonite clay. Exfoliated and intercalated materials with different maghnite loading in the range 3–15 wt % were investigated. ¹H NMR evidences Brønsted acid hydroxyl groups in the silicate layers and shows that their broad signal at 7.6 ppm present in the parent clay disappears in the nanocomposite material. ²⁷Al MAS NMR results show that beside the hexacoordinated aluminum signal, two additional peaks corresponding to two different tetrahedral Al sites are present in the clay framework. The NMR signal intensity of only one of them was found to be affected in the nanocomposites compared with the parent maghnite, suggesting that these specific aluminum sites are the reactive ones at the initial stages of the polymerization. However almost no changes occurred in the ²⁹Si NMR spectra, confirming that the polymer grafting, as indicated earlier by atomic force microscopy, took place on the aluminum tetracoordinated sites rather than on the silicon sites. A mechanism of maghnite surface catalyzed polymerization of ε‐caprolactone was proposed, involving Brønsted and Lewis acid sites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3060–3068, 2007     

Synthesis and characterization of poly(ethylene oxide‐co‐ethylene carbonate) macromonomers and their use in the preparation of crosslinked polymer electrolytes

Methacrylate‐functionalized poly(ethylene oxide‐co‐ethylene carbonate) macromonomers were prepared in two steps by the anionic ring‐opening polymerization of ethylene carbonate at 180 °C, with potassium methoxide as the initiator, followed by the reaction of the terminal hydroxyl groups of the polymers with methacryloyl chloride. The molecular weight of the polymer went through a maximum after approximately 45 min of polymerization, and the content of ethylene carbonate units in the polymer decreased with the reaction time. A polymer having a number‐average molecular weight of 2650 g mol^?1 and an ethylene carbonate content of 28 mol % was selected and used to prepare a macromonomer, which was subsequently polymerized by UV irradiation in the presence of different concentrations of lithium bis(trifluoromethanesulfonyl)imide salt. The resulting self‐supportive crosslinked polymer electrolyte membranes reached ionic conductivities of 6.3 × 10^?6 S cm^?1 at 20 °C. The coordination of the lithium ions by both the ether and carbonate oxygens in the polymer structure was indicated by Fourier transform infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2195–2205, 2006     

Solid state reactions of nitrogenous heterocyclic compounds(Ⅰ)——Solid state reactions of 3-methyl-l-phenyl-5-pyrazolone with carbonyl compounds

The solid state reaction of 3-methyl-1-phenyl-5-pyrazolone (MPP) with aromatic aldehydes and ke-tones benzil derivatives and imides,and the solid state Michael addition reaction of MPP with 4-arylidene-3-methyl-1-phenyl-5-pyrnzolone 2 were investigated.Some new solid state reactions between the reactants were found,from which a series of new compounds were obtained The structures of the products were identified by IR,1H NMR,MS,elemental analyses and also by X-ray crystal analysis,and the reaction mechanism of MPP with aromatic aldehydes and ketones was proposed     

Non isothermal heat capacities and chemical reactions using a modulated DSC

An evaluation of measurements of heat capacities by modulated differential scanning calorimetry, MDSC is presented. Heat capacities were obtained from 130 to 550 K by a non isothermal technique in which a periodic modulation was added to the linear heating rate. Effects of amplitude and period of modulation, sample weight, sample type, pan type, and cell imbalance are described. Results are compared with those obtained using the isothermal technique. Heat capacity could be measured well into the decomposition region and separated from the non reversing signal due to chemical reaction (degradation), thus allowing a precise detection of onsets of the thermal degradation. This additional information will aid in the interpretation of the degradation chemistry, a field vital for the petroleum-industry.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayPart of this paper was presented at the 23rd Conference of the North American Thermal Analysis Society, Toronto, Canada, September 25–28, 1994.The author (MVN) acknowledges the experimental assistance provided by J. Balogh of Exxon Research and Engineering Company, Linden. Helpful discussions with A. Boller of the University of Tennessee at Knoxville, Dr. Y. Jin, General Electrical, and Dr. S. Sauerbrunn formerly of TA Instruments are also acknowledged.     

Solid Phase Synthesis of 4H-Pyrimido[2,1-b] Benzothiazol-4-ones from Resin-Bound Cyclic Malonic Ester

The solid phase synthesis of 4H-pyrimido[2,1-6] benzothizaol-4-ones has been reported.     

Where are the Sn atoms in LaSb2Snx, 0.1?x?∼0.75?

The composition range and (composite modulated) structure of compounds within the wide range non-stoichiometric LaSb₂Sn_x, 0.1?x?0.75, solid solution is carefully investigated via a combined electron diffraction, XRD and electron probe microanalysis study. Evidence for metastability of the LaSb₂Sn_x phase at the low x composition end of the solid solution is presented. Direct evidence is found for a reasonably (although by no means perfectly) well ordered Sn sub-structure which is, in general, mutually incommensurable with respect to a very well ordered underlying LaSb₂ sub-structure along both a and c directions. The overall (3+2)-d superspace group symmetry is given along with a discussion of the consequences as regards the arrangement of the Sn atoms. The Sn sub-structure c-axis cell dimension shows very little variation with composition x providing direct experimental evidence of the importance of Sn-Sn metallic bonding (along one-dimensional [001] Sn strings) for the stability of the phase.     

Conformational changes of the amyloid beta-peptide (1-40) adsorbed on solid surfaces

The conformational change of the 39-43 residues of the amyloid beta-peptide (Abeta) toward a beta-sheet enriched state promotes self-aggregation of the peptide molecules and constitutes the major peptide component of the amyloid plaques in Alzheimer patients. The crucial question behind the self-aggregation of Abeta is related to the different pathways the peptide may take after cleavage from the amyloid precursor proteins at cellular membranes. This work is aiming at determining the conformation of the Abeta (1-40) adsorbed on hydrophobic Teflon and hydrophilic silica particles, as model sorbent surfaces mimicking the apolar transmembrane environment and the polar, charged membrane surface, respectively. The mechanism by which the Abeta interacts with solid surfaces strongly depends on the hydrophobic/hydrophilic character of the particles. Hydrophobic and electrostatic interactions contribute differently in each case, causing a completely different conformational change of the adsorbed molecules on the two surfaces. When hydrophobic interactions between the peptide and the sorbent prevail, the adsorbed Abeta (1-40) mainly adopts an alpha-helix conformation due to H-bonding in the apolar part of the peptide that is oriented towards the surface. On the other hand, when the peptide adsorbs by electrostatic interactions beta-sheet formation is promoted due to intermolecular association between the apolar parts of the adsorbed peptide. Irrespective of the characteristics of the solid sorbent, crowding the surface results in intermolecular association between adsorbed molecules leading to a strong aggregation tendency of the Abeta (1-40). [Diagram: see text] CD spectra of Abeta (1-40) at pH 7: A) in solution ([Abeta]=0.2 mg.ml(-1)) freshly prepared (line) and after overnight incubation (symbols);B) on Teflon (Gamma=0.5 mg.m(-2)).