28 research outputs found

    Synthesis by ATRP of Polystyrene-b-Poly(4-vinylpyridine) and Characterization by Inverse Gas Chromatography

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    A linear diblock copolymer [Polystyrene-b-Poly(4-vinyl-pyridine)] (PS-b-P4VP) was successfully prepared through Atom Transfer Radical Polymerization (ATRP). This synthesis is performed in two successive steps: using the (1-bromoethyl) benzene as initiatorand and Hexamethyl tris [2(dimethylamino)ethyl] amine as ligands in a protic solvent. The first step of the synthesis allows the realization of block polystyrene having a terminal function; however, Bromine (Br) permits the grafting of the second successive block P4VP. RMN -1H demonstrates that the P4VP block has been grafted onto the PS block. The molecular weight of PS-b-P4VP is determined by size exclusion chromatography, and its thermal stability is examined by TGA. The surface and the thermodynamic properties of this copolymer are studied by inverse gas chromatography (IGC). The new Hamieh Model shows that the synthesized copolymer PS-P4VP has an amphoteric behavior with rather very basic character that is six times stronger than acidic character (in Lewis terms), reflected the presence of acidic and basic groups in the structure of the PS-P4VP copolymer, more particularly the presence of benzenic, methyl and vinylpyridine groups

    Synthesis of lead-free (Bi0,5Na0,5)TiO3 thin film by RF magnetron sputtering: Impact of Na on the properties of film

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    International audienceThis work concerns the growth of (Bi0,5Na0,5)TiO3 on Si/SiO2/LNO by RF magnetron sputtering. We observed, for the first time on BNT thin films, reactions that destroy the film. This behavior is associated to sodium or sodium oxide segregation. After an extensive description of the sodium impact onto the film, a solution with adapted deposition conditions to suppress these effects is reported. Raising the sputter deposition temperature to 250 °C allows to have a pure perovskite BNT single phase. The ferroelectric, dielectric and piezoelectric properties of BNT films (thickness = 350 nm) were assessed. In particular, the macroscopic piezoelectric coefficient d33 attains a maximum value of 56 pm/V

    Interfacial viscoelastic moduli in a weak gel

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    HYPOTHESIS: The measurement of interfacial viscoelastic moduli provides information on the ability of surface-active agents to texture the interface. However, the contribution of the bulk rheology cannot be ignored in particular when the continuous phase exhibits a gel-like behavior, even with low modulus. EXPERIMENTS: Between 2 and 6 g/L, κ-carrageenan aqueous solutions have no significant activities at interfaces. At low concentrations or high temperatures, they behave like Newtonian liquids. Upon heating or cooling, a reversible liquid/gel transition appears with a hysteresis where the rheological behavior can be easily modulated by adjusting κ-carrageenan concentration. The frequency dependence of bulk and interfacial viscoelastic moduli are determined using a conventional shear rheometer and a drop tensiometer with a polyisobutene oil, respectively. FINDINGS: The effect of concentration and temperature is analyzed and the frequency dependence of interfacial moduli is correlated with those of the bulk. In presence of a gelled κ-carrageenan solutions, an elastic behavior of the interface appears and strengthens as the elastic modulus of the suspended phase is high. It turns out that the oscillating pendant drop method could be a sensitive indicator of the presence of very weak gels, even hardly detected by a shear classical rheometry

    Effect of Modulation and Functionalization of UiO-66 Type MOFs on Their Surface Thermodynamic Properties and Lewis Acid–Base Behavior

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    In this study, we investigated the surface thermodynamic properties of four MOF structures of the UiO-66 series, by employing seven molecular models, a thermal model, and three other methods using the inverse gas chromatography (IGC) technique at infinite dilution. We first determined the effect of the modulation of UiO-66 by an acid (e.g., formic acid and acetic acid) and on the other hand, we studied the effect of the functionalization of the organic linker by an amine group (NH2) on their dispersive component of the surface energy and on their Lewis acid–base properties. We found that all the studied MOFs presented an amphoteric character with a strong acidity whose acidity/basicity ratio is greater than 1 using all the models and methods in IGC. Moreover, the introduction of a modulator such as acetic acid or formic acid in the synthesis of these MOFs increased the number of structural defects and therefore increased the acidity of these MOFs. Similarly, the functionalization of the MOF by the NH2 group leads to an increase in the basicity constant of the functionalized MOF while remaining smaller than their acidity constant. In addition, the use of acids as modulators and amine groups as functional groups resulted in an increase in the dispersive component of the surface energy of the MOFs. Finally, comparing the results obtained by the different models and methods and based on the increasing order of the acidity of each MOF, it was clear that the thermal model resulted in more exact and precise values than the others. Our findings pave the way for the design and development of new acid catalysts based on UiO-66 structures

    Effect of Modulation and Functionalization of UiO-66 Type MOFs on Their Surface Thermodynamic Properties and Lewis Acid-Base Behavior

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    In this study, we investigated the surface thermodynamic properties of four MOF structures of the UiO-66 series, by employing seven molecular models, a thermal model, and three other methods using the inverse gas chromatography (IGC) technique at infinite dilution. We first determined the effect of the modulation of UiO-66 by an acid (e.g., formic acid and acetic acid) and on the other hand, we studied the effect of the functionalization of the organic linker by an amine group (NH2) on their dispersive component of the surface energy and on their Lewis acid-base properties. We found that all the studied MOFs presented an amphoteric character with a strong acidity whose acidity/basicity ratio is greater than 1 using all the models and methods in IGC. Moreover, the introduction of a modulator such as acetic acid or formic acid in the synthesis of these MOFs increased the number of structural defects and therefore increased the acidity of these MOFs. Similarly, the functionalization of the MOF by the NH2 group leads to an increase in the basicity constant of the functionalized MOF while remaining smaller than their acidity constant. In addition, the use of acids as modulators and amine groups as functional groups resulted in an increase in the dispersive component of the surface energy of the MOFs. Finally, comparing the results obtained by the different models and methods and based on the increasing order of the acidity of each MOF, it was clear that the thermal model resulted in more exact and precise values than the others. Our findings pave the way for the design and development of new acid catalysts based on UiO-66 structures

    Effect of amino functional groups on the surface properties and Lewis's acid base parameters of UiO-66(NH2) by inverse gas chromatography

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    Amino-functionalized metal organic frameworks (MOFs) have attracted much attention for various applications such as carbon dioxide capture, water remediation and catalysis. The focus of this study is to determine the surface and Lewis's acid-base properties of UiO-66(NH2) crystals by the inverse gas chromatography (IGC) technique at infinite dilution. The latter was applied to evaluate the dispersive component of the surface energy γsd(T) by using thermal model and several molecular models. The obtained results proved that γsd(T) decreases when the temperature increases. The best results were achieved by using the thermal model that takes into account the effect of the temperature on the surface areas of the organic molecules. We also observed a decrease of the Gibbs surface free energy of adsorption by increasing the temperature of the different organic solvents. The polar interactions of UiO-66(NH2) were obtained by using the methods of Saint-Flour Papirer, Donnet et al., Brendlé-Papirer and the different molecular models. The Lewis's acid base constants KA and KD were further calculated by determining the different variables of adsorption of the probes on the solid surface and the obtained values were 1.07 and 0.45 for KA and KD respectively, with an acid-base ratio (KA/KD) of 2.38. These values showed the high acidic surface of the solid substrate; whereas, the values of the entropic acid base parameters, ωA, ωD and ωA/ωD respectively equal to 1.0×10−3, 3.8×10−4 and 2.73, also highlighted the important acidity of UiO-66-(NH2) surface. These important findings suggest that the surface defects (missing linkers and/or clusters) in UiO-66(NH2) are the main determining factor of the acid-base properties of UiO-66 based structures
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