Fabienne Warmont

Internally structured pickering emulsions stabilized by clay mineral particles

The present study aims to describe emulsion particles containing a dispersed phase composed of nanostructured lipid mesophases and stabilized by montmorillonite and/or Laponite clay platelets. The size distributions of these emulsion particles were found independent of the clay mineral content and of the initial internal composition that determines the internal structure. The stabilization of the droplets by a shell of smectite layers was found possible even by montmorillonite which has a length of the same order or more than the droplets to stabilize. The clay platelets give a local flatness to the droplets that may influence the internal structure. In this paper, we describe the conditions to obtain such soft particles of about 220 nm, and we show by direct visualization the internal mesophase complexity and the shape of the particles. In particular, TEM analysis showed elongated particles with bent-back channels at their center but a different morphology at the periphery due to flat border conditions imposed by the presence of the clay minerals.

Poly(ethylene glycol)-stabilized silver nanoparticles for bioanalytical applications of SERS spectroscopy

The present work depicts the efficient one-step synthesis and detailed evaluation of stable aqueous colloids of silver nanoparticles (NPs) coated with poly(ethylene glycol) (PEG) covalently attached to their surface. Due to steric repulsion between polymer-modified surfaces, the stability of the nanoparticle suspension was preserved even at high ionic strength (0.1 M NaCl). At the same time, the PEG coating remains sufficiently permeable to allow surface-enhanced Raman scattering (SERS) from micromolar concentrations of small molecules such as the anticancer drug mitoxantrone (MTX). The enhancement efficiency of the hot spot-free Ag-PEG was compared to that of citrate-stabilized Ag colloids used after pre-aggregation. The potential of the polymer-stabilized colloids developed in this study is discussed in terms of bioanalytical applications of SERS spectroscopy.

Nonionic organoclay: A ‘Swiss Army knife’ for the adsorption of organic micro-pollutants?

A Na exchanged montmorillonite (Mt) was used as a starting layered material for the preparation of two organoclays synthesized with benzyl decyltrimethyl ammonium (BDTA) cationic surfactant and the tri-ethylene glycol mono n-decyl ether(C10E3), a nonconventional nonionic surfactant. The adsorption of the surfactants was performed at an amount of 0.7 times the cation exchange capacity (CEC) for BDTA and below the critical micelle concentration (cmc) where C10E3 is in a monomer state, leading to the intercalation of a lateral monolayer surfactant arrangement within the interlayer space and about 5-7% organic carbon content in organoclays. The environmental properties of both nonionic (C10E3Mt) and cationic (BDTAMt) organoclays were compared to those of the starting Mt clay with the sorption of three micro-pollutants: benzene, dimethyl-phthalate and paraquat. The adsorption isotherms and the derivative data determined through the fitting procedure by using Langmuir, Freundlich and Dubinin-Radushkevitch equation models explicitly highlighted the importance of the chemical nature of the micropollutants, which play on the adsorbents efficiency. The adsorption data combined with FTIR and XRD supplementary results suggest that C10E3Mt nonionic organoclay, although being less efficient for the retention of the different micropollutants, turned out to be the most polyvalent adsorbent since such hybrid material could adsorb the entire studied organic compounds.

Synthesis of novel ZnO/ZnAl2O4 multi co-centric nanotubes and their long-term stability in photocatalytic application

Based on the Kirkendall effect, novel double, triple and quadruple co-centric nanotubes of ZnO/ZnAl2O4 have been successfully fabricated by combining the two techniques of electrospinning and atomic layer deposition. The as-prepared samples were annealed at 900 °C under air. Their morphological, structural and optical properties were studied by Scanning Electron Microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Energy-Dispersive X-ray spectroscopy (EDX), UV-visible spectrophotometry, Raman spectroscopy, photoluminescence (PL) and reflectance emission. The performances and long-term stability of these multi co-centric nanotubes for photocatalytic applications have been evaluated under the same conditions. As result, in the photodegradation of methyl orange (MO) under UV irradiation, the triple and quadruple co-centric nanotubes of ZnO/ZnAl2O4 exhibit a higher photodegradation efficiency (94% and 99%, respectively) in repeated and long-term applications compared to the pure ZnO which has very low long-term photocatalytic stability. Thus, the fact of coupling these two semiconductors ensured a high photocatalytic activity and long term stability.

A novel and easy chemical-clock synthesis of nanocrystalline iron–cobalt bearing layered double hydroxides

A novel synthesis of cobalt-iron layered double hydroxide (LDH) with interlayer chlorides was investigated. The method consists in mixing concentrated solutions of hexaamminecobalt(III) trichloride with ferrous chloride at room temperature and in anoxic conditions. Four initial Fe/Co atomic ratios have been tried out (0.12, 0.6, 1.2 and 1.8). Neither heating nor addition of alkali was employed for adjusting the pH and precipitating the metal hydroxides. Still, each mixture led to the spontaneous precipitation of a LDH-rich solid having a crystal-chemistry that depended on the initial solution Fe/Co. These LDHs phases were carefully characterized by mean of X-ray diffraction, (57)Fe Mössbauer spectrometry, transmission electron microscopy and chemical analysis (total dissolution and phenanthroline method). Solution Eh and pH were also monitored during the synthesis. Increasing initial Fe/Co ratio impacted the dynamic of the observed stepwise reaction and the composition of the resulting product. Once the two solutions are mixed, a spontaneous and abrupt color change occurs after an induction time which depends on the starting Fe/Co ratio. This makes the overall process acting as a chemical clock. This spontaneous generation of CoFe-LDH arises from the interplay between redox chemistries of iron and cobalt-ammonium complexes.

Alteration of nanocrystalline calcium silicate hydrate (C-S-H) at pH 9.2 and room temperature: a combined mineralogical and chemical study

Abstract Calcium silicate hydrate (C-S-H) alteration was studied with flow-through experiments at 25°C and pH 9.2. Three materials with apparent Ca/Si ratios (C/S ratios) of 1.47, 1.38 and 0.86 were investigated. Physical (thermogravimetric analyses/differential thermal analysis), mineralogical (X-ray diffraction) and chemical (electron probe microanalysis, transmission electron microscopy/energy dispersive X-ray spectrometry) analyses were performed to characterize the reacting minerals. Initial stoichiometric C/S ratios were 1.22, 1.22 and 0.85, respectively. The excess of Ca is attributed mainly to the presence of calcium hydroxide intimately mixed in with C-S-H particles. The C-S-H chemical compositions were monitored during flow-through experiments in order to determine the mineral stoichiometry needed for reaction kinetics. Under our experimental conditions the stoichiometric C/S ratios decreased continuously with time. A close to stoichiometric dissolution was observed after 2 days of experiments. Using an integrated approach, the kinetics was found to be a function of the C/S. A decrease in layer-to-layer distance in the early stage of the alteration process is interpreted as interlayer Ca/Na exchange (Na being part of the pH buffering solution). A second dissolution step, marked by a close to stoichiometric release of Ca and Si, undoubtedly results from layer dissolution. The structural similarity of C-S-H and tobermorite was confirmed.

Dissolution kinetics of hydrated calcium aluminates (AFm-Cl) as a function of pH and at room temperature

Abstract The determination of reliable weathering/dissolution rates for cement phases is of fundamental importance for the modelling of the temporal evolution of both radioactive waste repositories and CO2 geological storage sites (e.g. waste matrix, plug in boreholes). Here, the dissolution kinetics of AFm-Cl (hydrated calcium aluminates containing interlayer Cl) has been studied using flow-through experiments conducted at pH values ranging from 9.2 to 13. Mineralogical (XRD) and chemical (EPMA, TEM) analyses have been performed to determine the evolution of the phases during the dissolution experiments. For pH values between 10 and 13, the dissolution of AFm-Cl is congruent (i.e. Ca/Al ratios close to 2 both for solids and outlet concentrations). In contrast, the precipitation of amorphous Al-phases and possibly amorphous mixed Al/Ca phases is observed at pH 9.2, leading to Ca/Al ratios in the outlet solutions higher than those of the initial solid. Therefore, at pH 9.2, even if Cl-/OH- exchange occurs, estimation of dissolution rate from released Cl appears to be the best proxy. Dissolution rates were normalized to the final specific surface areas (ranging from 6.1 to 35.4 m2 g−1). Dissolution rate appears to be pH-independent and therefore the far-from-equilibrium dissolution rate at room temperature is expressed as: logR(mol m-2 s-1) = -9.23 ± 0.18

Water Mobility within Compacted Clay Samples: Multi-Scale Analysis Exploiting 1H NMR Pulsed Gradient Spin Echo and Magnetic Resonance Imaging of Water Density Profiles

1H NMR pulsed gradient spin echo attenuation and water density profile analysis by magnetic resonance imaging are both used to determine the mobility of water molecules confined within a porous network of compacted kaolinite clay sample (total porosity of ∼50%). These two complementary experimental procedures efficiently probe molecular diffusion within time scales varying between milliseconds and few hours, filling the gap between the time scale of diffusion dynamics measured by traditional quasi elastic neutron scattering and through-diffusion methods. Furthermore, magnetic resonance imaging is a nondestructive investigation tool that is able to assess the effect of the local structure on the macroscopic mobility of the diffusing probe.