Laurent J. Michot

Mechanism of adsorption and desorption of water vapor by homoionic montmorillonites; 2, The Li (super +) , Na (super +) , K (super +) , Rb (super +) and Cs (super +) -exchanged forms

Methods previously used to distinguish between water adsorbed on external surfaces and in the interlamellar space of Na-montmorillonite during adsorption and desorption of water vapor have been extended to a set of homoionic Li-, Na-, K-, Rb- and Cs-montmorillonite. The textural and structural features have been investigated at different stages of hydration and dehydration using controlled-rate thermal analysis, nitrogen adsorption volumetry, water adsorption gravimetry, immersion microcalorimetry and X-ray powder diffraction under controlled humidity conditions. During hydration, the size of the quasi-crystals decreases from 33 layers to 8 layers for Na-montmorillonite and from 25 layers to 10 layers for K-montmorillonite, but remains stable around 8–11 layers for Cs-montmorillonite. Each homoionic species leads to a one-layer hydrate, which starts forming at specific values of water vapor relative pressure. Li-, Na- and K-montmorillonite can form a two-layer hydrate. By comparing experimental X-ray diffraction patterns with theoretically simulated ones, the evolution of structural characteristics of montmorillonites during hydration or desorption can be described. Using structural and textural data, it is shown that during adsorption: (1) the rate of filling of interlamellar space of the one layer hydrate increases with the relative pressure but decreases with the size of the cations; and (2) the different hydrated states are never homogeneous.

Mechanism of adsorption and desorption of water vapor by homoionic montmorillonite; 3, The Mg (super 2+) , Ca (super 2+) , and Ba (super 3+) exchanged forms

The swelling of some well-defined Mg-, Ca-, Sr- and Ba- homoionic montmorillonites was studied in the domain of water relative pressures lower than 0.95. This involves the expansion of the crystal lattice itself, commonly known as the “interlamellar expansion” or “inner crystalline swelling”. The initial freeze-dried clays were characterized by nitrogen adsorption-desorption volumetry and controlled transformation rate thermal analysis. The evolution of the structural and textural properties of these different clays at different stages of hydration and dehydration was investigated using water adsorption gravimetry, immersion microcalorimetry at different precoverage water vapor relative pressures and X-raydiffraction (XRD) under controlled humidity conditions. Large textural variations are observed in the dry state depending on the exchangeable cations. The 2-layer hydrate exhibits the most ordered layer stacking. Water is mainly adsorbed in the interlamellar space. With increasing water pressure, each homoionic species leads to a 1-layer hydrate and, with the exception of Ba-montmorillonite, to a predominant 2-layer hydrate. The relative pressure corresponding to the formation of the 2-layer hydrate decreases with increasing hydration energy of the interlayer cation. For Ca-, Sr- or Mg-montmoriHonites, simulation of XRD patterns leads to the definition of successive homogeneous states corresponding to the 2-layer hydrate. Furthermore, it yields the water filling ratio corresponding to the different hydration states during adsorption and desorption of water vapor.

Liquid–crystalline aqueous clay suspensions

This article demonstrates the occurrence of a true isotropic/nematic transition in colloidal Brownian aqueous suspensions of natural nontronite clay. The liquid–crystalline character is further evidenced by polarized light microscopy and small-angle x-ray scattering experiments in the presence and absence of modest external magnetic fields. The complete phase diagram ionic strength/volume fraction then exhibits a clear biphasic domain in the sol region just before the gel transition in contrast with the situation observed for other swelling clays in which the sol/gel transition hinders the isotropic/nematic transition. Small-angle x-ray scattering measurements of gel samples reveal strong positional and orientational orders of the particles, proving unambiguously the nematic character of the gel and, thus, clearly refuting the still prevalent “house of cards” model, which explains the gel structure by means of attractive interactions between clay platelets. Such order also is observed in various other swelling clay minerals; therefore, this very general behavior must be taken into account to reach a better understanding of the rheological properties and phase behavior of these systems.

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.

Adsorption of chlorinated phenols from aqueous solution by surfactant-modified pillared clays

New pillared clay-based adsorbents have been prepared by incorporating a nonionic surfactant of general formula C12–14H25–29O(CH2CH2O)5H (commercial name, Tergitol 15S-5), during the synthesis of the aluminum hydroxide pillaring reagent. Different loadings of surfactant have been examined. The presence of the surfactant enhanced the adsorption capacity of the clay toward 3-monochlorophenol from aqueous solution. On the basis of adsorption results for a series of clays with increasing surfactant loadings, the best adsorbent was obtained at a surfactant loading of 255 mg/g of clay. At this loading, the surfactant occupies the micropores, as well as the mesopores and the external surfaces of the pillared clay. Analysis of the adsorption isotherms for 3-monochlorophenol, 3,5-dichlorophenol, 3,4,5-trichlorophenol and pentachlorophenol at different pH shows that the most energetic adsorption sites are the surfactant-occupied micropores between pillars. Additional binding of chlorinated phenols occurs at surfactant sites on external surfaces and mesopores. Upon calcination at 500°C, the clay is converted to a conventional alumina-pillared clay with a basal spacing near 16 Å. This calcined product can be reused as an adsorbent for chlorinated phenols by readsorbing fresh surfactant. The recycled adsorbent exhibits performance properties comparable to the original adsorbent. These results demonstrate the feasibility of utilizing a surfactant-modified pillared clay as a recyclable adsorbent and combustion catalyst for environmental pollutants.

Fe, Mg and Al distribution in the octahedral sheet of montmorillonites. An infrared study in the OH-bending region

Abstract Ten montmorillonites of different origins with variable Fe contents were analysed using transmission IR spectroscopy. Special attention was devoted to the OH-bending region to obtain information about the distribution of octahedral cations. For low to medium Fe contents (≤ 0.56 per Si8 formula unit), a linear relationship between the position of the δAlFeOH band and Fe content was observed. Such correlation might be explained by changes in the cis-trans occupancy of Fe in the octahedral sheet. Deconvolution of the OH-bending domain allows us to discriminate three components (δAlAlOH, δAlMgOH and δAlFeOH) which are correlated with cation abundances derived from chemical analysis. The relative area of each band can then be compared with theoretical areas calculated assuming a fully random distribution of cations in the octahedral sheet. Using such treatment, eight of the 10 montmorillonites studied presented a nearly randomized octahedral distribution. The two samples from Wyoming were clearly different as they exhibited a strong ordering tendency.

Identification of nickel chelators in three hyperaccumulating plants: An X-ray spectroscopic study

We have investigated the accumulation of nickel in a hyperaccumulating plant from the Brassicacae family Leptoplax emarginata (Boiss.) O.E. Schulz. Two supplementary hyperaccumulating plants, which have been the subject of a high number of publications, Alyssum murale Waldst. & Kit and Thlaspi caerulescens J.&C. Presl, and a nonaccumulating species Aurinia saxatilis were also studied for reference. The plants were grown during 4 months in specific rhizoboxes with Ni-bearing minerals as a source of nickel. Nickel speciation was analyzed through X-ray absorption spectroscopy at Ni K-edge (X-ray absorption near edge spectroscopy and extended X-ray absorption fine structure spectroscopy) in the different parts of the plants (leaves, stems and roots) and compared with aqueous solutions containing different organo-Ni(II) complexes. Carboxylic acids (citrate, malate) appeared as the main ligands responsible of nickel transfer within those plants. Citrate was found as the predominant ligand for Ni in stems of Leptoplax and Alyssum, whereas in leaves of the three plants, malate appeared as the chelating organic acid of accumulated metal. Histidine could not be detected either in leaves, stems nor roots of any studied plant sample.

Liquid-crystalline nematic phase in aqueous suspensions of a disk-shaped natural beidellite clay.

After size-selection and osmotic pressure measurements at fixed ionic strength, the behavior of aqueous colloidal suspensions of anisotropic disklike beidellite clay particles has been investigated by combining optical observations under polarized light, rheological, and small angle X-ray scattering (SAXS) experiments. The obtained phase diagrams (volume fraction/ionic strength) reveal, for ionic strength below 10(-3) M/L, a first-order isotropic/nematic (I/N) phase transition before gel formation at low volume fractions, typically around 0.5%. This I/N transition line displays a positive slope for increasing ionic strength and shifts toward lower volume fraction with increasing particle size, confirming that the system is controlled by repulsive interactions. The swelling laws, derived from the interparticle distances obtained by SAXS, display a transition from isotropic swelling at low volume fractions to lamellar swelling at higher volume fractions. The liquid-crystal properties have then been investigated in detail. Highly aligned nematic samples can be obtained in three different ways, by applying a magnetic field, an ac electric field, and by spontaneous homeotropic anchoring on surfaces. The birefringence of the fluid nematic phase is negative with typical values around 5 x 10(-4) at a volume fraction of about 0.6%. High nematic order parameters have been obtained as expected for well-aligned samples. The nematic director is aligned parallel to the magnetic field and perpendicular to the electric field.

MIGRATION OF CATIONS IN COPPER(II)-EXCHANGED MONTMORILLONITE AND LAPONITE UPON HEATING

Two clay minerals, a dioctahedral, Na-montmorillonite from Wyoming and a trioctahedral, synthetic Na-laponite, were exchanged by cupric (Cu(II)) ions and subsequently heated at 100 °C intervals up to 500 °C. The resulting materials were analyzed by chemical analysis, X-ray diffraction (XRD), cation exchange capacity (CEC) measurements, combined thermogravimetric and differential thermal analysis (TGA-DTA), infrared (IR) spectroscopy, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS). Montmorillonite exhibits a well-known Hoffmann-Klemen effect in that, when heated, cupric (Cu) ions migrate into the lacunae of the octahedral sheet, where they compensate the negative charge deficit of the clay layer. In the case of laponite, CEC measurements and spectroscopic measurements reveal that Cu ions migrate into the octahedral sheet where they replace Li and Mg ions. After heating at 200 °C, approximately half the interlayer Cu ions are exchanged. The exchange appears to be 1 Cu for 1 Li, resulting in a slight decrease of the negative charge of the layer. After heating at 300 °C, the remaining Cu ions are exchanged by either 1 Mg or 2 Li, which does not result in any further charge reduction. At 400 °C, some of the extracted Mg remigrates into the structure and exchanges some Li (1 Mg for 2 Li). The final product at 400 or 500 °C is then a Li-laponite with Cu(II) in the octahedral sheet.

Aqueous suspensions of natural swelling clay minerals. 1. Structure and electrostatic interactions.

In this article, we present a general overview of the organization of colloidal charged clay particles in aqueous suspension by studying different natural samples with different structural charges and charge locations. Small-angle X-ray scattering experiments (SAXS) are first used to derive swelling laws that demonstrate the almost perfect exfoliation of clay sheets in suspension. Using a simple approach based on geometrical constraints, we show that these swelling laws can be fully modeled on the basis of morphological parameters only. The validity of this approach was further extended to other clay data from the literature, in particular, synthetic Laponite. For all of the investigated samples, experimental osmotic pressures can be properly described by a Poisson-Boltzmann approach for ionic strength up to 10(-3) M, which reveals that these systems are dominated by repulsive electrostatic interactions. However, a detailed analysis of the Poisson-Boltzmann treatment shows differences in the repulsive potential strength that are not directly linked to the structural charge of the minerals but rather to the charge location in the structure for tetrahedrally charged clays (beidellite and nontronites) undergoing stronger electrostatic repulsions than octahedrally charged samples (montmorillonites, laponite). Only minerals subjected to the strongest electrostatic repulsions present a true isotropic to nematic phase transition in their phase diagrams. The influence of ionic repulsions on the local order of clay platelets was then analyzed through a detailed investigation of the structure factors of the various clay samples. It appears that stronger electrostatic repulsions improve the liquidlike positional local order.