Serge Lagerge

Polymer-surfactant interactions: binding mechanism of sodium dodecyl sulfate to poly(diallyldimethylammonium chloride).

The binding mechanism of poly(diallyldimethylammonium chloride), PDAC, and sodium dodecyl sulfate, SDS, has been comprehensively studied by combining binding isotherms data with microcalorimetry, zeta potential, and conductivity measurements, as well as ab initio quantum mechanical calculations. The obtained results demonstrate that surfactant-polymer interaction is governed by both electrostatic and hydrophobic interactions, and is cooperative in the presence of salt. This binding results in the formation of nanoparticles, which are positively or negatively charged depending on the molar ratio of surfactant to PDAC monomeric units. From microcalorimetry data it was concluded that the exothermic character of the interaction diminishes with the increase in the surfactant/polymer ratio as well as with an increase in electrolyte concentration.

Adsorption of benzoic acid from organic solvents on calcite and dolomite: Influence of water

Abstract A study has been carried out of the adsorption of benzoic acid from cyclohexane solution onto the hydrophilic surface of calcite. We determined initially the chemical and mineral composition of the solid, its specific surface area and its granulometry. This was followed by the determination of the enthalpies of immersion of calcite in different solvents. These thermodynamic properties gave information on the energetics of calcite—solvent interactions. In this way, we could construct a scale of affinities of the different organic molecules and water for the calcite surface. It was noted that the enthalpies were higher in unsaturated than in saturated organic solvents, and higher in water than in the organic solvents. The adsorption isotherms and the differential molar enthalpies of displacement were determined in the presence and the absence of water. The role played by water in the adsorption of polar organic molecules from the oil phase has not been clearly explained previously. In this paper, we indicate how the presence of water can modify the adsorption of aromatic compounds on the surface of calcite. As regards the adsorption isotherms, the presence of water essentially increases the amount of adsorption. The results of the calorimetric studies were found to be surprising; we observed that the differential molar enthalpies of displacement were endothermic. Similar experiments were carried out with dolomite and n-heptane solution and the results compared with those obtained with calcite and cyclohexane, leading to the formulation of a general model concerning the adsorption of small polar organic molecules from organic solvents onto the surfaces of the carbonates.

Small-Angle Neutron Scattering Study of Solubilization of Tributyl Phosphate in Aqueous Solutions of L64 Pluronic Triblock Copolymers

We have studied the solubilization behavior of tributylphosphate (TBP) in aqueous solutions of L64-Pluronics, using light and small angle neutron scattering (SANS). Varying the temperature and the oil content, the system presents a nontrivial phase behavior. In particular, at 308 K, a first solubilization followed by an emulsification failure and a resolubilization is found. We have measured the microstructure by SANS and characterized the microemulsion droplet core size, corona thickness, polydispersity, and interactions. It is shown that at low oil content, the system is made of small swollen micelles. After the phase separation, the resolubilization is carried by larger oil droplets decorated by copolymer. From specific surface measurements at large angles, a surprising change in surfactant conformation is found to accompany this morphological evolution which is also supported by previous results obtained from ¹H NMR experiments. In independent measurements, our structural modeling is confirmed using contrast-variation SANS.

Calorimetric methods applied to the investigation of divided systems in colloid science

AbstractA new batch titration microcalorimeter has been used for estimation of thermodynamic properties in various investigated colloidal systems. As examples, we present enthalpic and kinetic data obtained from this calorimetric device for four different processes widely encountered in colloid science: (i)The dilution/micellization process of cationic gemini surfactants in aqueous solution.(ii)The hydration process of non ionic surfactants in organic solution, i.e. the mechanism of micellar solubilization of water in the aggregates.(iii)The complexation of calcium ions by polyacrylates sodium salts (PaNa).(iv)The adsorption phenomenon of PaNa molecules on the calcium carbonate surface.

Native and hydrophobized human IGG: Enthalpies of heat-induced structural changes and adsorption onto silica

Differential scanning calorimetry (DSC) and isothermal calorimetric batch technique were used to monitor the heat-induced structural changes and adsorption properties of human immunoglobulin G (IgG), in native and hydrophobized states. The transition temperature (Tmax) and enthalpy of heat-induced conformational changes (ΔcalH) of IgG in solution as well as the enthalpy change accompanying the adsorption of IgG onto hydrophilic silica (ΔadsH), were shown to depend on the degree of the protein hydrophobicity (number of covalently attached alkyl chains). The adsorption enthalpy for all forms of IgG at all surface concentrations was found to be endothermic, that is the process is entropy driven. Factors affecting the IgG adsorption onto silica are discussed.

Adsorption of A Multifunctional Additive (ZnDTC) Onto Iron and Iron(III) Oxide from n-Decane

The adsorption of zinc diisooctylodithiocarbamate (ZnDTC) onto iron and iron(III) oxide from n-decane solution was studied. The adsorption isotherms were determined together with the variation of the apparent differential molar enthalpy of displacement for ZnDTC on both adsorbents at 298 K. The shapes of the iostherms for the adsorption of dithiocarbamate on iron and iron(III) oxide are quite different, especially in the low coverage ratio. The corresponding differential molar enthalpies of displacement for the two studied systems are exothermic. On iron, the very high exothermic values indicate a process of ZnDTC chemisorption, while on iron(III) oxide, the much lower enthalpic effects are characteristic of physisorption.