Benedicte Prelot

Layer charge and electrophoretic mobility of smectites

The aim of this study is to determine the effect of the layer charge of smectites on their electrophoretic mobility (EM), using electrophoresis measurements. In order to cover the charge domain from 0 to 2 charges per unit structural cell, two clay series were used: thermally treated Cu-montmorillonite (0-0.7) and synthetic saponites (0.7-2). All the studied samples are negatively charged in a pH range from 2 to 12. Neither layer charge nor ionic strength influences the EM of smectites at neutral to alkaline pH. At acidic pH, the EM of smectites ranges from −3 to −0.4 10−8 m2 s−1 V−1 when the layer charge ranges from 0.8 to 2. High charge and low charge smectites, which are not expandable, tend to aggregate in aqueous suspension, and the measured EM corresponds then to the amphoteric sites of the edge faces of the layer stacks. These sites are negatively charged at pH values above 3.

Morphology and surface heterogeneities in synthetic goethites

In the framework on a study of the acido-basic and sorption properties of iron oxides, a thorough characterization of two types of goethite powders was performed in several laboratories joined in a common project. Chemical analysis by ICPAES; high-resolution SEM, TEM, and AFM observations; XRD with line width analysis; and argon and nitrogen sorption isotherms were used for that purpose. The main crystallographic faces of goethite particles could be identified as {001}, {101}, and {121}, and their abundance correlated with the distribution of low-pressure argon adsorption local isotherms. These results will be very useful for further studies on the relationship between surface reactivity in aqueous solution and orientation of solid surfaces.

Structural–chemical disorder of manganese dioxides: 1. Influence on surface properties at the solid–electrolyte interface

Relationships between lattice parameters of manganese dioxides and their surface properties at the solid-aqueous solution interface were investigated. The studied series ranged from ramsdellite to pyrolusite and encompassed disordered MD samples. The structural model used takes into account structural defects: Pr (rate of pyrolusite intergrowth) and Tw (rate of microtwinning). Water adsorption isotherms showed that the cross sectional area of water molecules adsorbed in the first monolayer is positively correlated to Pr. Titration of the surface charge of the MD series evidenced a positive linear relationship between the PZC and Pr (Pr=0, Tw=0, PZC=1 for ramsdellite; Pr=1, Tw=0, PZC=7.3 for pyrolusite; gamma-MD with intermediate values of Pr (0.2 to 0.45) have increasing PZC values). The rate of microtwinning appeared as a secondary factor for the increase of the PZC. The above correlations are explained by the chemical defects at the origin of the structural disorder, respectively Mn(3+)/Mn4+ substitution for Pr and Mn vacancies for Tw, which result in proton affinity and thus in increased PZC. The experimental results are compared with data collected in the literature for manganese dioxides as well as for dioxides of transition elements with tetragonal structure.

Structural–chemical disorder of manganese dioxides

Relationships between lattice parameters of manganese dioxides and their surface properties at the solid-aqueous solution interface were investigated. The studied series ranged from ramsdellite to pyrolusite and encompassed disordered MD samples. The structural model used takes into account structural defects: Pr (rate of pyrolusite intergrowth) and Tw (rate of microtwinning). Water adsorption isotherms showed that the cross sectional area of water molecules adsorbed in the first monolayer is positively correlated to Pr. Titration of the surface charge of the MD series evidenced a positive linear relationship between the PZC and Pr (Pr=0, Tw=0, PZC=1 for ramsdellite; Pr=1, Tw=0, PZC=7.3 for pyrolusite; gamma-MD with intermediate values of Pr (0.2 to 0.45) have increasing PZC values). The rate of microtwinning appeared as a secondary factor for the increase of the PZC. The above correlations are explained by the chemical defects at the origin of the structural disorder, respectively Mn(3+)/Mn4+ substitution for Pr and Mn vacancies for Tw, which result in proton affinity and thus in increased PZC. The experimental results are compared with data collected in the literature for manganese dioxides as well as for dioxides of transition elements with tetragonal structure.

Structural–chemical disorder of manganese dioxides: II. Influence on textural properties

Relationships between structural parameters of MnO2 and their surface properties at the solid-gas interface were investigated. The studied series ranged from ramsdellite to pyrolusite and encompassed disordered gamma-MnO2 samples. The structural model used takes into account structural defects: Pr (rate of pyrolusite intergrowth in the ramsdellite network) and Tw (rate of microtwinning). Analysis of the N2 adsorption isotherm evidenced positive correlations between specific surface area and Tw for gamma-MnO2 only and between the energetic constant C and (1-Pr). No microporosity is evidenced. Water adsorption isotherms evidenced the dependence of the H2O monolayer volume on Tw and showed a positive correlation between the cross-section area of water molecules adsorbed in the first monolayer and Pr, ranging from 13.5 A2 for Pr=1 to 6.3 A2 for Pr=0.2 (12 sites/nm2). Energetic heterogeneity is quantified from Ar and N2 low-pressure adsorption isotherms with the DIS procedure and correlated with H2O adsorption. High-energy adsorption domains are quantified and assigned to the different crystal faces: (110) faces with a common 1 x 1 octahedra layer of pyrolusite and ramsdellite and the (001) face of ramsdellite with 2 x 2 octahedra on which channels and plateaus are differentiated. The specific surface area ratio of ramsdellite high-energy sites to total ramsdellite content is shown to depend on Tw. The dependence on microtwinning of low cross-sectional area of N2 and much lower cross-sectional of residual H2O molecules leads us to assume that their adsorption sites on grain boundaries are represented by the twin planes between the structured nanocrystals generated by oxygen evolution during MD synthesis.

Driving force for the hydration of the swelling clays: Case of montmorillonites saturated with alkaline-earth cations

Important structural modifications occur in swelling clays upon water adsorption. The multi-scale evolution of the swelling clay structure is usually evidenced by various experimental techniques. However, the driving force behind such phenomena is still not thoroughly understood. It appears strongly dependent on the nature of the interlayer cation. In the case of montmorillonites saturated with alkaline cations, it was inferred that the compensating cation or the layer surface could control the hydration process and thus the opening of the interlayer space, depending on the nature of the interlayer cation. In the present study, emphasis is put on the impact of divalent alkaline-earth cations compensating the layer charge in montmorillonites. Since no experimental technique offers the possibility of directly determining the hydration contributions related to interlayer cations and layer surfaces, an approach based on the combination of electrostatic calculations and immersion data is developed here, as already validated in the case of montmorillonites saturated by alkaline cations. This methodology allows to estimate the hydration energy for divalent interlayer cations and therefore to shed a new light on the driving force for hydration process occurring in montmorillonites saturated with alkaline-earth cations. Firstly, the surface energy values obtained from the electrostatic calculations based on the Electronegativity Equalization Method vary from 450 mJ m(-2) for Mg-montmorillonite to 1100 mJ m(-2) for Ba-montmorillonite. Secondly, considering both the hydration energy for cations and layer surfaces, the driving force for the hydration of alkaline-earth saturated montmorillonites can be attributed to the interlayer cation in the case of Mg-, Ca-, Sr-montmorillonites and to the interlayer surface in the case of Ba-montmorillonites. These results explain the differences in behaviour upon water adsorption as a function of the nature of the interlayer cation, thereby allowing the macroscopic swelling trends to be better understood. The knowledge of hydration processes occurring in homoionic montmorillonites saturated with both the alkaline and the alkaline-earth cations may be of great importance to explain the behaviour of natural clay samples where mixtures of the two types of interlayer cation are present and also provides valuable information on the cation exchange occurring in the swelling clays.

Manganese Dioxides Surface Properties Studied by XPS and Gas Adsorption

Structurally well defined γ-MnO 2 in terms of Pr and Tw were studied using X-ray photoelectron spectroscopy (XPS) to complete surface investigations performed by high-resolution gas adsorption, water adsorption, and acid-base surface titration. The O Is s and Mn 2p spectra were deconvoluted into three components Mn-OH + 2 , Mn-OH, and Mn-O - . Analysis of the O Is spectra in energy shift and relative intensity shows that 70 to 80% of the surface groups stay as neutral OH, 5% as Mn-OH 2 and 20 to 30% as Mn-OH: their relative amount varies with Pr as well as PZC, water cross-sectional area and energetic constant C. Mn 2p spectra are far less sensitive than O is to the charge variation. Nevertheless a correlation is shown between the relative amount of surface species, the binding energy of Mn = O and O = Mn species and Tw.

Micellization Behavior of Long-Chain Substituted Alkylguanidinium Surfactants.

Surface activity and micelle formation of alkylguanidinium chlorides containing 10, 12, 14 and 16 carbon atoms in the hydrophobic tail were studied by combining conductivity and surface tension measurements with isothermal titration calorimetry. The purity of the resulting surfactants, their temperatures of Cr→LC and LC→I transitions, as well as their propensity of forming birefringent phases, were assessed based on the results of 1H and 13C NMR, differential scanning calorimetry (DSC), and polarizing microscopy studies. Whenever possible, the resulting values of Krafft temperature (TK), critical micelle concentration (CMC), minimum surface tension above the CMC, chloride counter-ion binding to the micelle, and the standard enthalpy of micelle formation per mole of surfactant (ΔmicH°) were compared to those characterizing alkyltrimethylammonium chlorides or bromides with the same tail lengths. The value of TK ranged between 292 and 314 K and increased strongly with the increase in the chain length of the hydrophobic tail. Micellization was described as both entropy and enthalpy-driven. Based on the direct calorimetry measurements, the general trends in the CMC with the temperature, hydrophobic tail length, and NaCl addition were found to be similar to those of other types of cationic surfactants. The particularly exothermic character of micellization was ascribed to the hydrogen-binding capacity of the guanidinium head-group.

Self-organization in water of well-defined amphiphilic poly(vinyl acetate)-b-poly(vinyl alcohol) diblock copolymers

A series of well-defined poly(vinyl acetate)-b-poly(vinyl alcohol) (PVAc-b-PVA) amphiphilic diblock copolymers with different hydrophilic block sizes were synthesized by a combination of macromolecular design via the interchange of xanthates (MADIX) polymerization and copper-catalyzed Huisgens click reaction (CuAAC). Poly(vinyl acetate)s were first prepared by MADIX polymerization using new chain transfer agents bearing clickable moieties. After the hydrolysis of PVAc homopolymers under basic conditions, PVAc-b-PVA copolymers were synthesized using Huisgens reaction with copper catalysis. Then, the self-assembly in water of PVAc-b-PVA was studied by dynamic light scattering (DLS), static light scattering (SLS), pyrene fluorescence and isothermal titration calorimetry (ITC). The dependence between the hydrophilic chain length of the copolymer and the critical aggregation concentration (CAC) value has been proved. The three different methods of characterization showed similar results, the CAC increasing with hydrophilic block length. Additionally, ITC has proved to be a very valuable technique for the study of self-organization of amphiphilic copolymers.

Filtration–elution of Cryptosporidium oocysts assisted by electrostatic interactions

Abstract The goal of the present study was to investigate the interfacial phenomena that govern the interactions between Cryptosporidium parvum oocysts and synthetic filtration media, in order to define guidelines to improve the choice of appropriate materials and filtration–elution conditions. Three frequently used filtration media were studied: polycarbonate and cellulose-ester membranes, and a polyethersulfone cartridge. The electrokinetic potential of Cryptosporidium oocysts and of the filtration media were measured by electrophoresis and streaming potential, respectively. Aqueous media such as dilutions of a phosphate buffer (PBS), NaCl, CaCl 2 at various concentrations and pH, were tested. The highest recovery rates, close to 100%, were obtained in conditions where the electrokinetic potentials of both the membrane and the oocysts were at maximum negative values. This condition was met using a polycarbonate membrane and low concentrations of monovalent salt. The media generally used in microbiology, such as phosphate buffer or 8 g l −1 KCl or NaCl, caused irreversible adhesion and dramatic decrease in recovery rates.