X-ray diffraction study of the structure of carboxymethylcellulose-cationic surfactant complexes.

We have investigated dilute aqueous solutions of an anionic polymer (carboxymethylcellulose) mixed with cationic surfactants of different chain lengths (dodecyl to octadecyl trimethylammonium bromides: DTAB, TTAB, CTAB and OTAB). The structures of the concentrated phases formed above the precipitation threshold were studied by X-ray diffraction. Different body-centred cubic structures with space groups Pm3n were observed in the presence of surfactant with a short aliphatic chain (DTAB), despite the fact that the polymer persistence length is comparable to the repeat distance of the structure (5 nm). For larger surfactant chain lengths (TTAB and CTAB), the structure of the precipitates can be either cubic (Pm3n) or 2D hexagonal depending on the initial surfactant and polymer concentrations. For still larger chain length (OTAB), the structure becomes lamellar. This structural evolution from micellar cubic towards 2D hexagonal and lamellar is attributed to the decrease of the local curvature of the surfactant aggregates, as observed for flexible synthetic polymers and short DNA fragments under similar conditions. Furthermore, the structure of the bulk complexes formed just below the precipitation threshold anticipates the structure seen in the precipitated phases.     

Stability of filled poly(dimethylsiloxane) and poly(diphenylsiloxane-co-dimethylsiloxane) elastomers to cyclic stress at elevated temperature

The response of aluminum oxide-filled poly(dimethyl siloxane) and poly(diphenylsiloxane-co-dimethylsiloxane) elastomers, containing 3–24 mol % diphenylsiloxane, to cyclic stress at elevated temperatures (dynamic creep) was evaluated. The materials could be divided into two classes, based on their response to the application of cyclic stress: no or low-diphenylsiloxane content elastomers in which substantial creep and a decrease in crosslink density were observed, and high diphenylsiloxane content (16–24 mol %) elastomers that showed decreased creep with increasing diphenylsiloxane content and an increase in crosslink density. It was suggested that the phenyl groups stabilize the siloxane bond in the polymer backbone, decreasing the rate of chain scission reactions as the diphenylsiloxane content increases and stabilizing the elastomer against creep. The balance of chain scission, chemical crosslinking, and cyclic formation reactions varies depending on diphenylsiloxane content, giving rise to the differences in dynamic creep behavior. An activation energy of 12.9 kcal/mol was measured for dynamic creep of poly(16% diphenylsiloxane/84% dimethyl siloxane), suggesting that a catalyzed degradation mechanism was responsible. The primary catalysts of the degradation reactions are postulated to be the filler particles. © 1996 John Wiley & Sons, Inc.     

Magnetic and Mössbauer data of Fe in K2ZnF4, analyzed in the spin Hamiltonian formalism

Magnetic measurements on single crystals and Mössbauer spectra of powders under magnetic field, recorded on Fe²⁺ doped K₂ZnF₄, have been analyzed in the spin Hamiltonian formalism. The data slightly depart from the expectations of a spin 2 in D_4h symmetry. The occurrence of vibronic effects is discussed.     

Steric stabilization of polystyrene colloids using thiol-ended polyethylene oxide

Thiol-ended polyethylene oxide (I) has been prepared from the esterification of thioglycolic acid with monomethylether of polyoxyethylene glycol. Emulsion polymerization of styrene (and, in a few cases, methylmethacrylate as comonomer) was carried out in the presence of I using either water-soluble azo initiator or t-butylhydroperoxide. In the former case, bimodal particle size distribution was obtained while monodisperse latexes could be prepared in the latter case. Then a redox system was formed from I and t-BuOOH so that I was both an initiator and a transfer agent. Good steric stabilization of the latexes was observed. The polyethylene oxide sequence of I was partly incorporated at the surface of the latex particles, but the incorporation yield remained limited (between 7 and 18%). Most of the resdue of I remained in the serum.     

Large deformations during the coalescence of fluid interfaces

Surface forces and shape changes were simultaneously measured during the approach and coalescence of two liquid-liquid and liquid-air interfaces. Large normal and lateral deformations were observed that are nevertheless consistent with a simple theoretical analysis of the long-range effects of short-range attractive van der Waals forces. The results imply that two fluidlike structures such as liquid droplets and soft biological cells can sense each other at much larger separations than previously assumed based on criteria taken from the interactions of hard particles.     

A tetranuclear Cr(III)Ni(II)3 cyano-bridged complex based on M(tacn) derivative building blocks

The reaction of Cr(Bztacn)(CN)3 (Bztacn is 1,4,7-trisbenzyl-1,4,7-triazacyclononane) with Ni(iPrtacn)Cl2 (iPrtacn is 1,4,7-trisisopropyl-1,4,7-triazacyclononane) affords a CrNi3 tetranuclear complex. Variable temperature and magnetization versus field measurements show a S = 9/2 ground state and an appreciable magnetic anisotropy with a negative D(9/2) value equal to -0.54 cm(-1). Magnetization studies on one single crystal using a micro-SQUID show a fast tunneling process at zero field at very low temperature.     

L'électron habillé non relativiste dans un champ magnétique

We consider a nonrelativistic electron interacting with a classical magnetic field pointing along the $x_3$-axis and with a quantized electromagnetic field. Because of the translation invariance along the $x_3$-axis, we consider the reduced Hamiltonian associated with the total momentum along the $x_3$-axis and, after introducing an ultraviolet cutoff and an infrared regularization, we prove that the reduced Hamiltonian has a ground state if the coupling constant and the total momentum along the $x_3$-axis are sufficiently small. Finally, we determine the absolutely continuous spectrum of the reduced Hamiltonian and we prove that the renormalized mass of the electron is greater than its bare one. To cite this article: L. Amour et al., C. R. Acad. Sci. Paris, Ser. I 340 (2005).     

A new method for the absolute measurement of piezoelectric coefficients on thin polymer films

A new quasistatic method to measure piezoelectric coefficients on thin polymer films is presented. This method is based on a combined experimental/analytical approach, where small polymer samples (6 mm x 3 mm x 110 microm) are encapsulated in a soft silicone rubber and an electric field is applied across their thickness (3-direction). Strains are measured optically along three perpendicular directions using a laser Doppler vibrometer, and the experimental measurements are used in a Rayleigh-Ritz energy minimization procedure implemented symbolically in MATHCAD, which yields the absolute piezoelectric coefficients d(3ii). These measured coefficients are material properties of the polymer and do not depend on the specific boundary conditions of the problem. The validity of the method is established using the ATILA finite element code. Experimental values of d(311), d(322), and d(333) obtained for polyvinylidene fluoride (PVDF) at room temperature, in the frequency range 500-2000 Hz, are presented and compared with existing data; excellent agreement is found. The extension of the method to the determination of electrostrictive coefficients on soft polyurethane materials is introduced.