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91.
Francisco Rodríguez-González José Pérez-González Lourdes de Vargas Benjamín M. Marín-Santibáñez 《Rheologica Acta》2010,49(2):145-154
The continuous extrusion of a metallocene linear low-density polyethylene through a transparent capillary die with and without
slip was analyzed in this work by rheometrical measurements and particle image velocimetry (PIV). For this reason, a comparison
was made between the rheological behaviors of the pure polymer and blended with a small amount of fluoropolymer polymer processing
additive. Very good agreement was found between rheometrical and PIV measurements. The pure polymer exhibited stick-slip instabilities
with nonhomogeneous slip at the die wall, whereas the blend showed stable flow. The slip velocity was measured directly from
the velocity profiles and was negligible for the pure polymer before the stick-slip but increased monotonously as a function
of the shear stress for the blend. The flow curves and the slip velocity as a function of the shear stress deviated from a
power law and were well fitted by continuous “kink” functions. Comparison of PIV data with rheometrical ones permitted a direct
proof of the basic assumption of the Mooney theory. Finally, the analysis of the velocity profiles showed that there is a
maximum in the contribution of slip to the average fluid velocity, which is interpreted as the impossibility for the velocity
profile to become plug like in the presence of shear thinning. 相似文献
92.
Julien Férec Marie-Claude Heuzey José Pérez-González Lourdes de Vargas Gilles Ausias Pierre J. Carreau 《Rheologica Acta》2009,48(1):59-72
The behavior of short glass fiber–polypropylene suspensions in extensional flow was investigated using three different commercial
instruments: the SER wind-up drums geometry (Extensional Rheology System) with a strain-controlled rotational rheometer, a
Meissner-type rheometer (RME), and the Rheotens. Results from uniaxial tensile testing have been compared with data previously
obtained using a planar slit die with a hyperbolic entrance. The effect of three initial fiber orientations was investigated:
planar random, fully aligned in the stretching flow direction and perpendicular to it. The elongational viscosity increased
with fiber content and was larger for fibers initially oriented in the stretching direction. The behavior at low elongational
rates showed differences among the various experimental setups, which are partly explained by preshearing history and nonhomogenous
strain rates. However, at moderate and high rates, the results are comparable, and the behavior is strain thinning. Finally,
a new constitutive equation for fibers suspended into a fluid obeying the Carreau model is used to predict the elongational
viscosity, and the predictions are in good agreement with the experimental data. 相似文献
93.
Rocío Esquembre María Lourdes Renart Jos Antonio Poveda C. Reyes Mateo 《Molecules (Basel, Switzerland)》2022,27(19)
The nanostructuration of solid matrices with lipid nanoparticles containing membrane proteins is a promising tool for the development of high-throughput screening devices. Here, sol-gel silica-derived nanocomposites loaded with liposome-reconstituted KcsA, a prokaryotic potassium channel, have been synthesized. The conformational and functional stability of these lipid nanoparticles before and after sol-gel immobilization have been characterized by using dynamic light scattering, and steady-state and time-resolved fluorescence spectroscopy methods. The lipid-reconstituted KcsA channel entrapped in the sol-gel matrix retained the conformational and stability changes induced by the presence of blocking or permeant cations in the buffer (associated with the conformation of the selectivity filter) or by a drop in the pH (associated with the opening of the activation gate of the protein). Hence, these results indicate that this novel device has the potential to be used as a screening platform to test new modulating drugs of potassium channels. 相似文献
94.
Dr. Iñigo Bretos Dr. Ricardo Jiménez Dr. Jesús Ricote Prof. M. Lourdes Calzada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(42):9277-9291
Photochemistry has emerged in the last few years as a powerful tool for the low-temperature processing of metal oxide thin films prepared by solution methods. Today, its implementation into the fabrication procedure makes possible the integration of amorphous semiconductors or functional crystalline oxides into flexible electronic systems at temperatures below 350 °C. In this review, the effects of UV irradiation at the different stages of the chemical solution deposition of metal oxide thin films are presented. These stages include from the synthesis of the precursor solution to the formation of the amorphous metal-oxygen network in the film and its subsequent crystallization into the oxide phase. Photochemical reactions that can be induced in both the solution deposited layer and the irradiation atmosphere are first described, highlighting the role of the potential reactive chemical species formed in the system under irradiation, such as free radicals or oxidizing compounds. Then, the photochemical effects of continuous UV light on the film are shown, focusing on the decomposition of the metal precursors, the condensation and densification of the metal-oxygen network, and the nucleation and growth of the crystalline oxide. All these processes are demonstrated to advance the formation and crystallization of the metal oxide thin film to an earlier stage, which is ultimately translated into a lower temperature range of fabrication. The reduced energy consumption of the process upon decreasing the processing temperature, and the prospect of using light instead of heat in the synthesis of inorganic materials, make photochemistry as a promising technique for a sustainable future ever more needed in our life. 相似文献
95.
Dissociation of the two amide protons from complexes of asymmetric diaminodiamides with Ni(II) in aqueous solution occurs under moderately basic conditions. The loss of the protons is accompanied by a conversion of the complex from octahedral to square planar. The rates of conversion for complexes NiL2+ were measured spectrophotometrically and were found to depend linearly on [OH?]. The diaminodiamide ligands used were S, R, S- and S, S, S-N, N′-dialanylpropylenediamine (DAPN), S, S-N, N′-dialanylethylenediamine (DAEN), R-N, N′-diglycylpropylenediamine (DGPN), and N, N′-diglycylethylenediamine (DGEN). The rates varied in the order SS-DAEN > DGEN > SRS-DAPN > R-DGPN ≈ SSS-DAPN. 相似文献
96.
Lourdes Ventol Valerie Metivaud Laura Bays Raül Benages Miquelngel Cuevas‐Diarte Teresa Calvet Denise Mondieig 《Helvetica chimica acta》2006,89(9):2027-2039
Complementary techniques had to be applied to investigate the binary system tetradecanedioic acid (C14H26O4)–hexadecanedioic acid (C16H30O4), because all the forms observed have the same space group (P21/c; Z = 2). We studied the polymorphism of the two single compounds and of their mixtures by X‐ray powder diffraction, differential‐scanning calorimetry (DSC), infrared spectroscopy (IR), scanning electron microscopy (SEM), and thermo‐optical microscopy (TOM). The two diacids were found to be isopolymorphic. At low temperature, they crystallize in the same ordered C‐form, and, on heating, adopt the ordered Ch‐form, 1° below their melting point. In contrast to similar compounds (unbranched alkanes, alkanols, and fatty acids), the solid–solid and solid–liquid phase‐transition temperatures decrease with increasing chain length. At low temperature, a new monoclinic form, Ci, appears as a result of the disorder of composition in the mixed samples. There are two [C + Ci]‐type solid–solid domains. On heating, the solid domains are related to solid–liquid domains by a peritectic invariant for compositions rich in C14H26O4, and by a eutectic invariant for compositions rich in C16H30O4. At higher temperature, there appears a second peritectic invariant for compositions rich in C14H26O4, together with a metatectic invariant for compositions rich in C16H30O4. All the solid forms observed in this binary system are isostructural. Nevertheless, the equilibrium between them is complex near the melting point, and their miscibility in the solid state is reduced. 相似文献
97.
Elena Junquera Lourdes Peña Emilio Aicart 《Journal of inclusion phenomena and macrocyclic chemistry》1996,24(3):233-239
The molecular encapsulation of sodium perfluoroctanoate (SPFO) by hydroxypropyl--cyclodextrin (HP--CD) or 2,6-di-O-methyl--cyclodextrin (DM--CD) has been analyzed by measuring the conductivity in solution of the ternary systems formed by CD + SPFO + H2O. The studies were carried out at 25 °C using a fully computerized electrical conductivity technique. The measurements were made as a function of CD concentration at various non-micellar concentrations of SPFO, and as a function of CD and SPFO concentrations with [CD]/[SPFO] constant at stoichiometric ratio. The inclusion complexes, HP--CD-SPFO and DM--CD-SPFO, were characterized through the stoichiometry, which has been found to be 1 : 1 in both cases, and the binding constants, which have been evaluated from the conductivity data with a model proposed by us considering the variation of the ionic molar conductivities with the concentration and the association of the surfactant counterion to the inclusion complex. The resultingK values indicate that the interaction between the CD cavity and the monomeric SPFO is strong and similar in both cases. 相似文献
98.
This work describes the adsorption behavior of associating and non-associating chains and their mixtures in pores with activated surfaces. The systems are studied using Gibbs ensemble Monte Carlo molecular simulations. Fluid molecules are modeled as freely jointed Lennard-Jones chains. Associating chains have, additionally, an associating square-well site placed in an end sphere. The pores are modeled as regular slit pores via an integrated Lennard-Jones potential (10-4-3); activation is achieved by placing specific association sites protruding from the surface. Two different solid-fluid interaction parameters are used, one of which corresponds roughly to alkanes on graphite, the other being a much weaker interaction. Adsorption isotherms are presented for several different cases: associating and non-associating chains confined within both neutral and activated walls. Mixtures of associating and non-associating chains are also considered. The effects of pore size, temperature and chain length are quantified. Selectivities obtained are in the range of those seen in adsorption experiments of alkane-alkanol mixtures. 相似文献
99.
Herdes C Santos MA Medina F Vega LF 《Langmuir : the ACS journal of surfaces and colloids》2005,21(19):8733-8742
We combine here a regularization procedure with individual adsorption isotherms obtained from grand canonical Monte Carlo simulations in order to obtain reliable pore size distributions. The methodology is applied to two hexagonal high-ordered silica materials: SBA-15 and PHTS, synthesized in our laboratory. Feasible pore size distributions are calculated through an adaptable procedure of deconvolution over the adsorption integral equation, with two necessary inputs: the experimental adsorption data and individual adsorption isotherms, assuming the validity of the independent pore model. The application of the deconvolution procedure implies an adequate grid size evaluation (i.e., numbers of pores and relative pressures to be considered for the inversion, or kernel size), the fulfillment of the discret Picard condition, and the appropriate choice of the regularization parameter (L-curve criteria). Assuming cylindrical geometry for both porous materials, the same set of individual adsorption isotherms generated from molecular simulations can be used to construct the kernel to obtain the PSD of SBA-15 and PHTS. The PSD robustness is measured imposing random errors over the experimental data. Excellent agreement is found between the calculated and the experimental global adsorption isotherms for both materials. Molecular simulations provide new insights into the studied systems, pointing out the need of high-resolution isotherms to describe the presence of complementary microporosity in these materials. 相似文献
100.
José Sepúlveda-Arques Mercedes Medio-Simón Lourdes Piqueres-Vidal 《Monatshefte für Chemie / Chemical Monthly》1989,120(12):1113-1118
Summary 1-tert-Butyl-4-vinylpyrazole1 a reacts with dimethyl acetylenedicarboxylate (DMAD), methyl propiolate (MP) and N-phenylmaleimide (NPMI) affording the indazole derivatives2,3, and5 as a result of a Diels-Alder ([4 + 2]) cycloaddition. With diethylazodicarboxylate (DEAZD), tetracyanoethylene (TCNE) and 4-phenyl-1,2,4-triazole-3,5-dione (PTAD) the reaction takes place exclusively through the olefinic substituent and the adducts6,7, and9 were isolated. The alkenylpyrazoles1 b–d reacted withDMAD and N-phenylmaleimide to give polymers.
Cycloadditionen von 1-tert-Butyl-4-vinylpyrazol
Zusammenfassung 1-tert-Butyl-4-vinylpyrazol1 a reagiert mit Acetylendicarbonsäure-dimethylester (DMAD), Propiolsäuremethylester (MP) und N-Phenylmaleimid (NPMI) zu den entsprechenden Indazolderivaten2,3 bzw.5, als Ergebnis einer Diels-Alder-([4+2])-Cycloaddition. Bei der Reaktion mit Azodicarbonsäure-diethylester (DEAZD), Tetracyanethylen (TCNE) und 4-Phenyl-1,2,4-triazol-3,5-dion (PTAD) wird exklusiv die Olefingruppe von1 a angegriffen, wobei die Addukte6,7 bzw.8 isoliert werden. Die Alkenylpyrazole1 b–d reagieren mitDMAD und N-Phenylmaleimid unter Bildung von Polymeren.相似文献