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51.
Igor Kosacki Vladimir Petrovsky Harlan U. Anderson Philippe Colomban 《Journal of the American Ceramic Society》2002,85(11):2646-2650
The results of Raman-scattering studies of nanocrystalline CeO2 and ZrO2 :16% Y (YSZ) thin films are presented. The relationship between the lattice disorder and the form of the Raman spectra is discussed and correlated with the microstructure. It is shown that the Raman line shape results from phonon confinement and spatial correlation effects and yields information about the material nonstoichiometry level. 相似文献
52.
A Sulzer SMX mixer was used to disperse gas into viscous, Newtonian and non-Newtonian fluids. The investigation covered the effect of the dispersed phase volume fraction, the viscosity of the continuous phase, the mixer length and the power draw. The flow regime was kept laminar in all the experiments. The dispersion of gas was carried out with gas concentrations between 1% and 7% in volume. Using the “process viscosity” concept, it was possible to collapse all the measured sizes on a single master curve by using the energy consumption in the mixer as the common variable between the experiments. Comparison was made with a Kenics mixer. The SMX mixer was found to be better adapted to the dispersion task due to its internal structure. 相似文献
53.
54.
Structure and functional complementation of engineered fragments from yeast phosphoglycerate kinase 总被引:1,自引:0,他引:1
Pecorari Frederic; Minard Philippe; Desmadril Michel; Yon Jeannine M. 《Protein engineering, design & selection : PEDS》1993,6(3):313-324
Previous studies have shown that, although the isolated structuraldomains of yeast phosphoglycerate kinase recover a quasi-nativestructure in vitro as well as in vivo, they do not reassociatenor generate a functional enzyme. The aim of this work was firstto study the folding of complementary fragments different fromstructural domains and second to determine the requirementsfor their reassociation and functional complementation. Themethod used for producing rigorously defined fragments consistsof the introduction of a unique cysteinyl residue in the proteinfollowed by a specific cleavage by 5'5'-dithiobis(2-nitrobenzoate)/potassiumcyanide at this residue. Two pairs of complementary fragmentswere thus obtained, 196/97415 and 1248/249415.The structure and stabilities of the different fragments werestudied. The short fragments, i.e. 196 and 249415were found to contain some secondary structure, but to havea low stability. Each large fragment has a high structural contentand a stability close to that of the corresponding domain. Incontrast to that observed with the isolated domains, a weakbut significant complementation was observed for the two pairsof fragments; the pair of fragments 1248/249415recovered 8% of the activity of the native enzyme upon complementation.An independent refolding of the complementary fragments beforereassociation decreased the yield of complementation for thepair of fragments 196/97415, but did not affectthe complementation for the other pair (1248/249415).From the present data and previous work on the isolated domains,it appears that the correct folding of the isolated fragmentsis not a prerequisite for their complementation. 相似文献
55.
C. G'sell V. Favier J. M. Hiver A. Dahoun M. J. Philippe G. R. Canova 《Polymer Engineering and Science》1997,37(10):1702-1711
The macroscopic stress-strain behavior of monoclinic polypropylene samples was investigated at 70°C under uniaxial tension and simple shear by means of a special videometric testing system that gives access to the constitutive equation of plastic behavior at constant strain rate up to large deformation. At several levels of plastic strain, the microstructural evolution of the material was characterized by means of X-ray scattering, densitometry and viscoelastic analysis. It appears that the strain hardening is high in tension, whereas it is nearly zero in shear. This behavior is associated with the development of a fiber texture in tension, which differs drastically from the planar crystalline texture developed in shear. Furthermore, it is shown that structural damage takes place as the plastic deformation proceeds in tension, while only little damage is recorded in shear. A viscoplastic model has been developed that specifically tales into account the various slip systems activated in the polypropylene crystallites and the elastic interactions of the lamellae through a self-consistent scheme. Simulations based on this model reproduce correctly the contrasting strain-hardening in tension and in shear and the different crystalline textures induced for these two loading paths. 相似文献
56.
Grard Delahay Stphane Kieger Nathalie Tanchoux Philippe Trens Bernard Coq 《Applied catalysis. B, Environmental》2004,52(4):251-257
The kinetics of the selective catalytic reduction (SCR) of NO by NH3 in the presence of O2 has been studied on a 5.5% Cu-faujasite (Cu-FAU) catalyst. Cu-FAU was composed of cationic and oxocationic Cu species. The SCR was studied in a gas phase-flowing reactor operating at atmospheric pressure. The reaction conditions explored were: 458<TR<513 K, 2503 (ppm) < 4000, 12 (%) < 4. The kinetic orders were 0.8–1 with respect to NO, 0.5–1 with respect to O2, and essentially 0 with respect to NH3. Based on these kinetic partial orders of reactions and elementary chemistry, a wide variety of mechanisms were explored, and different rate laws were derived. The best fit between the measured and calculated rates for the SCR of NO by NH3 was obtained with a rate law derived from a redox Mars and van Krevelen mechanism. The catalytic cycle is described by a sequence of three reactions: (i) CuI is oxidized by O2 to “CuII-oxo”, (ii) “CuII-oxo” reacts with NO to yield “CuII-NxOy”, and (iii) finally “CuII-NxOy” is reduced by NH3 to give N2, H2O, and the regeneration of CuI (closing of the catalytic cycle). The rate constants of the three steps have been determined at 458, 483, and 513 K. It is shown that CuI or “CuII-oxo” species constitute the rate-determining active center. 相似文献
57.
Emile M. Gaydou Philippe Bouchet 《Journal of the American Oil Chemists' Society》1984,61(10):1589-1593
The kernel fat content of 16 different mango varieties collected from the Northwestern part of Madagascar island were examined.
The fat content (22–54%) was determined by chloroform/methanol extraction. Investigation by gas liquid chromatography (GLC)
revealed 15 fatty acids, mainly palmitic (7–12%), stearic (22–40%), oleic (41–48%) and linoleic (7–17%). Significant correlations
were observed among the main fatty acids. Testing for the sterol fraction in 15 mango varieties allowed us to separate and
quantitatively analyze 7 sterols by GLC. The main sterols wereβ-sitosterol (47–76%), stigmasterol (12–23%) and campesterol (7–12%). The stigmasterol/campesterol ratio (1.2:2.3) was lower
in mango kernel fat than in cocoa butter. Among the 4-methyl sterol fractions, gramisterol, lophenol, obtusifoliol and citrostadienol
were tentatively identified by GLC. Lupeol, cycloartenol,α- andβ-amyrins and friedelinol were tentatively identified by GLC in the triterpene alcohols fractions. 相似文献
58.
Daniel Serrano Jean Peyrelasse Christian Boned Daniel Harran Philippe Monge 《应用聚合物科学杂志》1990,39(3):679-693
The percolation model has been applied to the study of gelation of the TGDDM-DDS system (tetraglycidyldiaminodiphenylmethane–diaminodiphenylsulfone) at a mass concentration of 100–30. For each temperature the experimental viscosity curves are satisfactorily described by a percolation law. Using the degree of chemical reactions, X, as a variable, a very clear change in the reaction mechanism with temperature can be shown. Then a rate of advancement of effective reactions, Y, is defined. This value only takes intermolecular-type reactions into account, and is probably the only variable on which viscosity depends in a percolation law: η = B(1 ? Y/Yc)?p. We obtain Yc= 0.45 and p= 2.0. Comparing Xc and Yc at the gel point, we obtain information on the proportion of intramolecular reactions with temperature. It is also demonstrated that the critical percolation threshold agrees closely with the gel point determined experimentally on log G″= f(t) curves. 相似文献
59.
This work is the fourth part of an overall project the aim of which was the development of general mix design rules for concrete containing different kinds of mineral admixtures. The two first parts presented the separation and quantification, by means of an empirical model based on semi-adiabatic calorimetry measurements, of the different physical effects responsible for changes in cement hydration (short terms) when chemically inert quartz powders were used in mortars. Part three dealt with an intensive experimental program, presenting and commenting more than 2000 compressive strength measurements. This program concerned 1 day to 6 months old mortars containing up to 75% of inert and pozzolanic admixtures. All these compressive strength results are analyzed in this fourth part and the influence of three effects, namely dilution, heterogeneous nucleation and the pozzolanic effect, are discriminated and quantitatively evaluated. An efficiency concept is proposed in order to take into account the effect of mineral admixture in mortars from both the physical and chemical points of view. It uses an efficiency function ξ(p) that has notable properties: it is independent of time, independent of fineness and independent of the type of mineral admixture. 相似文献
60.
The different low temperature coordination modes of ethylene and butadiene on a platinum (111) face, (110) face and on a palladium (111) face are compared on the basis of extended Hückel calculations. The nature of the chemical interaction between the olefin and the surface is detailed and the electronic factors that govern the coordination mode of the hydrocarbon are underlined. The different surfaces are modelled by a 49 or a 44 atoms cluster. A correction is applied in the calculation in order to minimize the artefact introduced by this cluster representation of an extended surface. For the adsorption, the respective importance of two electrons interactions and four electrons repulsions is the key point for the determination of the preferred mode. The di- coordination is more stable on platinum (111) but on the platinum (110) face the coordination yields the same adsorption energy than the di- one. This is roughly the same result for the palladium (111) face. The mode is there favored by a decrease of the four electrons repulsions caused either by a smaller number of metal neighbours for the surface atom (Pt(110)) or by a reduced radial expansion of the metal orbitals (Pd(111)). This coordination is associated with a smaller hybridization of the ethylene molecule. The results are extended to the adsorption of butadiene and this allows a qualitative explanation of the better selectivity for butadiene partial hydrogenation on palladium compared with platinum. 相似文献