M. L. Turco Liveri

Adsorption of triblock copolymers and their homopolymers at laponite clay/solution interface. Role played by the copolymer nature.

The adsorption thermodynamics of copolymers, based on ethylene oxide (EO) and propylene oxide (PO) units, at the laponite (RD) clay/liquid interface was determined at 298 K. The copolymer nature was tuned at molecular level by changing the hydrophilicity, the architecture and the molecular weight (Mw) keeping constant the EO/PO ratio. Polyethylene (PEGs) and polypropylene (PPGs) glycols with varying Mw and their mixture were also investigated to discriminate the role of the EO and the PO segments in the adsorption process. Enthalpies of transfer of RD, at fixed concentration, from water to the aqueous macromolecule solutions as functions of the macromolecule molality were determined. They were treated quantitatively by means of a model based on two equilibria: (1) one-to-one binding between the macromolecule and the site on the solid and (2) two-to-one binding following which one macromolecule interacts with another one adsorbed onto the solid. The good agreement between the equilibrium constants obtained from calorimetry and those determined from kinetic experiments confirmed the reliability of the experimental and theoretical approaches. Almost all of the systems investigated are highlighted by the one-to-one binding; the L35 and 10R5 systems present both equilibria. The insights provided by the thermodynamics of adsorption of their homopolymers onto RD were fruitful in obtaining detailed information on the nature of the forces involved between RD and the copolymers. The data obtained in the present work clearly evidenced that for comparable polymer Mw, PPG is more suitable in building up a steric barrier around the RD particles and, indeed, exhibits several advantages and no drawbacks. Moreover, the parent copolymers may properly functionalize the RD surface by exploiting both their high affinity to the solid surface and the ability to self-assemble onto it as L35 and 10R5 clearly showed.

Interactions of tetradecyldimethylaminoxide with polyacrylic and polymethacrylic acids in aqueous solution

Abstract The interactions between the zwitterionic surfactant tetradecyldimethylaminoxide (C14DMAO) and the polyelectrolytes polyacrylic (PAA-205 and PAA-250) or polymethacrylic (PMA-100) acids have been investigated in aqueous solution. The physico-chemical properties of these systems have been monitored by measuring the solution pH, electric birefringence, zero-shear viscosity and density for increasing surfactant concentrations. The experimental results have shown that significant change in the physico-chemical properties of the polyacid/surfactant system occurs only in a narrow pH range and when the amphiphile forms rod-like micelles. Moreover, they clearly reveal the important role played by both hydrogen bonding and hydrophobic forces in governing polyacid–surfactant interactions. The change in the physico-chemical properties of the polyacid solutions upon addition of C14DMAO has been attributed to both the conformational transition of the polyelectrolyte chains and the polyacid/rod-like micelles complex formation. The suggestion is made that the C14DMAO induces a progressive conformational transition in the polyelectrolyte chains much akin to that produced by NaOH.

Photocatalytic degradation of toluene in aqueous suspensions of polycrystalline TiO2 in the presence of the surfactant tetradecyldimethylamino-oxide

The heterogeneous photocatalytic method has been used for carrying out the toluene oxidation in synthetic aqueous solutions containing also a zwitterionic surfactant, i.e. tetradecyldimethylamino-oxide (C 14 DMAO). A batch photoreactor with immersed lamp and two kinds of polycrystalline TiO 2 catalysts were used. The results indicate a substantial increase of the toluene degradation rate in the presence of the surfactant; the complete photo- oxidation of toluene was achieved in a few hours of irradiation at the used experimental conditions; at higher irradiation times also C 14 DMAO was completely degraded. The main intermediates of toluene degradation were p-cresol (4-methyiphenol) and benzaldehyde. Depending on the used catalyst, benzyl alcohol, benzoic acid, hydroquinone, trans, trans muconic acid and pyrogallol (1,2,3 trihydroxybenzene) were also detected.

Calorimetric study of the solubilization of ethylenediamine, N,N-dimethylaminoethylamine and N,N,N′,N′-tetramethylethylenediamine by reversed AOT micelles

Distribution constants and standard enthalpies of transfer of ethylenediamine (en), N,N-dimethylaminoethylamine (dmen) and N,N,N′,N′-tetramethylethylenediamine (tmen) partitioned between n-heptane and water containing reversed sodium bis(2-ethylhexyl) sulfosuccinate (AOT) micelles as a function of the molar concentration ratio R (R=[water]/[AOT]) were evaluated by a calorimetric method. The results show that en, dmen and tmen molecules, solubilized in the reversed micelles, are distributed between the micellar aqueous core and the micellar palisade layer. An analysis of the thermodynamic parameters of the partition process demonstrates the peculiar solvent properties of the water containing reversed AOT micelles.

Dielectric properties of solutions of antimony (III) halides in methanol

The complex permittivities obtained by time domain reflectometry (TDR) measurements in the frequency range 0.1–15 GHz are reported for solutions of SbF3, SbCl3 and SbBr3 in methanol at 25°C. By increasing the concentration of the solutes, a marked increase of the main relaxation time and of the static permittivity of methanol is observed. These effects have been attributed to the ability of antimony (III) halides to strengthen the hydrogen bonding in methanol and to promote the shift of the dynamic equilibria among the various populations of hydrogen bonded methanol aggregates toward those characterized by a parallel orientation of neighboring dipoles. A second relaxation, occurring at low frequencies, was attributed to the rotational dynamics of the solvated solute molecules.

Calorimetric and viscosimetric investigation of the interaction between α,β-polyasparthydrazide and sodium dodecyl sulfate micelles

Abstract The interaction between α,β-polyasparthydrazide (PAHy) and sodium dodecyl sulfate (SDS) micelles in aqueous solution was investigated by calorimetry and viscosimetry. The dependence of the enthalpic effect due to this interaction upon the surfactant concentration was rationalized in terms of a progressive binding of SDS micelles to the polymeric backbone. The analysis of the calorimetric data allow evaluation of the binding ability of SDS micelles to the polymeric chain. The viscosimetric behavior of SDS plus PAHy aqueous solutions, discussed in terms of the parameter F [F = ηrel(PAHy) + ηrel(PAHy) − ηrel(SDS+PAHy)], confirms the occurence of the interaction between SDS micelles and the PAHy macromolecule.