In-situ SAXS study of aqueous clay suspensions submitted to alternating current electric fields.

Aqueous colloidal suspensions of clay platelets display a sol/gel transition that is not yet understood. Depending on the nature of the clay, liquid-crystalline behavior may also be observed. For example, the suspensions of beidellite display a nematic phase whereas those of montmorillonite do not. Both beidellite and montmorillonite have a "TOT" structure but the structural electric charge is located in the tetrahedral layer for the former and in the octahedral layer for the latter. We built a setup to perform SAXS experiments on complex fluids submitted to an electric field in situ. We found that the fluid nematic phase of beidellite suspensions readily aligns in the field. However, the field had no influence on the gels, showing that the orientational degrees of freedom of the platelets are effectively frozen. Moreover, strong platelet alignment was induced by the field in the isotropic phase of both clays, in a similar way, regardless of their ability to form a nematic phase. This surprising result would suggest that the orientational degrees of freedom are not directly involved in the sol/gel transition. The ability to induce orientational order in the isotropic phase of clay suspensions can be exploited to prepare materials of controlled anisotropy.

Tailoring highly oriented and micropatterned clay/polymer nanocomposites by applying an a.c. electric field.

Clay/polymer nanocomposites have recently raised much interest because of their widespread industrial applications. Nevertheless, controlling both clay platelet exfoliation and orientation during polymerization still remains challenging. Herein, we report the elaboration of clay/polymer nanocomposite hydrogels from aqueous suspensions of natural swelling clays submitted to high-frequency a.c. electric fields. X-ray scattering experiments have confirmed the complete exfoliation of the clay sheets in the polymer matrix, even after polymerization. Moreover, polarized light microscopy shows that the clay platelets were perfectly oriented by the electric field and that this field-induced alignment was frozen in by in situ photopolymerization. This procedure allowed us to not only produce uniformly aligned samples but also pattern platelet orientation, at length scales down to 20 µm. This straightforward and cheap nanocomposite patterning technique can be easily extended to a wide range of natural or synthetic inorganic anisotropic particles.

Elaboration and characterization of nanoliposome made of soya; rapeseed and salmon lecithins: application to cell culture.

Health benefits of unsaturated fatty acids have been demonstrated over the last decades. Nanotechnology provided new process to produce particles such as liposomes and nanoliposomes made of pure phospholipids. These techniques are already used in pharmaceutics to augment the bioavailability and the bioefficiency of drugs. The aim of this paper is to characterize and evaluate the potential of nanoliposomes made of three lecithins (soya, rapeseed and salmon) on cell culture in order to use them in the future as drug delivery systems for tissue engineering. We began to measure, with zetasizer, the radius size of liposomes particles which are 125.5, 136.7 and 130.3 nm respectively for rapeseed, soya and salmon lecithin. Simultaneously, solutions observed by TEM demonstrated the particles were made much of liposomes than droplet (emulsion). Finally, we found that the solutions of lecithins were enough stable over 5 days at 37 °C to be used in culture medium. We investigated the effect of soya, rapeseed and salmon lecithin liposome from 2mg/mL to 5.2 µg/mL on metabolic activity and cell proliferation on rat bone marrow stem cells (rBMSC) during 14 days. The results showed that the three lecithins (soya, rapeseed and salmon) improve cell proliferation at different concentration.

Aqueous suspensions of natural swelling clay minerals. 2. Rheological characterization.

We report in this article a comprehensive investigation of the viscoelastic behavior of different natural colloidal clay minerals in aqueous solution. Rheological experiments were carried out under both dynamic and steady-state conditions, allowing us to derive the elasticity and yield stress. Both parameters can be renormalized for all sizes, ionic strength, and type of clay using in a first approach only the volume of the particles. However, applying such a treatment to various clays of similar shapes and sizes yields differences that can be linked to the repulsion strength and charge location in the swelling clays. The stronger the repulsive interactions, the better the orientation of clay particles in flows. In addition, a master linear relationship between the elasticity and yield stress whose value corresponds to a critical deformation of 0.1 was evidenced. Such a relationship may be general for any colloidal suspension of anisometric particles as revealed by the analysis of various experimental data obtained on either disk-shaped or lath- and rod-shaped particles. The particle size dependence of the sol-gel transition was also investigated in detail. To understand why suspensions of larger particles gel at a higher volume fraction, we propose a very simplified view based on the statistical hydrodynamic trapping of a particle by an another one in its neighborhood upon translation and during a short period of time. We show that the key parameter describing this hydrodynamic trapping varies as the cube of the average diameter and captures most features of the sol-gel transition. Finally, we pointed out that in the high shear limit the suspension viscosity is still closely related to electrostatic interactions and follows the same trends as the viscoelastic properties.

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.

Orientational order of colloidal disk-shaped particles under shear-flow conditions: a rheological-small-angle X-ray scattering study.

The structure of a colloidal dispersion consisting of anisometric natural clay particles (beidellite) was followed under shear-flow conditions by small-angle X-ray scattering (SAXS) measurements in a Couette-type cell. It is shown that in this shear-thinning dispersion an orientational order develops with increasing shear rate. By use of two different geometrical configurations for SAXS measurements, corresponding to incident beam parallel and perpendicular to flow velocity gradient (radial and tangential configurations, respectively), it is observed that SAXS patterns are anisotropic in both geometries, meaning that particles tend to align along a preferred orientation with their normal in velocity gradient direction, and further they partly rotate around flow streamlines. Quantitative interpretation of these results is successfully achieved upon derivation of a probability distribution function accounting for biaxial particle orientation. From this distribution and following geometrical arguments, the viscosity of the suspension was calculated for each shear rate and found to correctly compare with rheological measurements, thereby appropriately relating the anisotropy of the SAXS patterns to macroscopic flow behavior of the suspension.

Highly concentrated emulsions: 1. Average drop size determination by analysis of incoherent polarized steady light transport.

The analysis of incoherent polarized steady light transport is reported as a convenient technique for the drop size determination in highly concentrated oil-in-water emulsions. The studied system consists in heptane-in-water emulsions stabilized with a copolymeric surfactant (Synperonic PE®/L64). Hundred grams of parent emulsions, at two volume fractions of dispersed phase (φ=0.958 and 0.937) were prepared using a semi-batch process. Then, they were diluted with the aqueous phase to obtain volume fractions ranging from 0.886 to 0.958. The use of a copolymeric surfactant allows the dilution of the highly concentrated emulsions without any change in the particle size distribution as confirmed by laser diffraction measurements. We found that the polarization technique allows the determination of the film thickness between water drops rather than their sizes. Consequently, we propose a geometrical relationship to determine an average drop size from the film thickness. The sensitivity of this alternative technique to detect changes in average drop size was studied by changing some process and formulation parameters. Drop size determination in highly concentrated emulsions via this method is useful since the measurement protocol neither involves dilution nor induces structural changes in the emulsion.

Sol-gel and isotropic/nematic transitions in aqueous suspensions of natural nontronite clay. Influence of particle anisotropy. 2. Gel structure and mechanical properties.

After size-selection, the phase behavior of aqueous suspensions of nontronite clay was analyzed by osmotic pressure measurements, rheological experiments, and small-angle X-ray scattering. All the measurements confirm that for ionic strength < or =10(-3) M/L, the system is purely repulsive. By combining results from osmotic pressure measurements and X-ray scattering, it appears that the pressure of the system can be well-described using a simple Poisson-Boltzmann treatment based on the interaction between charged infinite parallel planes. In terms of rheological properties, even if the status of the sol/gel transition remains partially unclear as the number density of particles at the sol-gel transition exhibits a -2 power dependence with average particle size, the yield stress and elasticity of the gels can be easily renormalized for all particle sizes on the basis of the volume of the particles. Furthermore, rheological modeling of the flow curves shows that for all the particles, an approach based on excluded volume effects captures most features of nontronite suspensions. Still, the high shear flow properties of the suspensions that reveal a strong orientation of particles in the flow are affected by electrostatic interactions. This study then shows that the rich phase behavior of clay minerals, notably the fact that some clay minerals display an isotropic/nematic transition while others exhibit a sol-gel transition, requires a full understanding of all the interactions in the system that can only be achieved by working on well-characterized size-selected samples.

Sol/gel and isotropic/nematic transitions in aqueous suspensions of natural nontronite clay. Influence of particle anisotropy. 1. Features of the i/n transition.

The phase behavior of a natural nontronite clay was studied for size-selected particles by combining osmotic pressure measurements, visual observations under polarized light, and rheological experiments. In parallel, the positional and orientational correlations of the particles were analyzed by small-angle X-ray scattering. Aqueous suspensions of nontronite exhibit a true isotropic/nematic (I/N) transition that occurs before the sol/gel transition, for ionic strengths below 10(-3) M/L. In this region of the phase diagrams, the system appears to be purely repulsive. The I/N transition shifts toward lower volume fractions for increasing particle anisotropy, and its position in the phase diagram agrees well with the theoretical predictions for platelets. SAXS measurements reveal the presence of characteristic interparticular distances in the isotropic, nematic, and gel phases. The swelling law (separation distance vs swelling law) exhibits two regimes. For high volume fractions, the swelling law is one-dimensional as in layered systems and reveals the presence of isolated platelets. At lower volume fraction, distances scale as phi(-1/3), indicating isotropic volumic swelling. Finally, the experimental osmotic pressure curves can be satisfactorily reproduced by considering the interparticle distances between two charged planes whose effective charge is around 10% of the structural charge.

Birefringence determination in turbid media.

We study the influence of birefringence on incoherent polarized light transport in turbid media. In particular, Mueller matrices backscattered by a diffusing medium are modified by the birefringence of the suspending phase. We study this effect both theoretically, through Monte Carlo simulations, and experimentally with a highly birefringent xanthane solution in which particles are added at various concentrations to modify its turbidity. Comparisons between experiments on flow-induced birefringence of the xanthane solution with or without particles are in good agreement and show the capability of measuring birefringence in turbid media through analysis of Mueller matrices.

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.

Size determination by use of two-dimensional Mueller matrices backscattered by optically thick random media.

Here we are concerned with the systematic study of polarized light transport in thick, isotropic, homogeneous random media and of the associated inverse problem. An original spatial and intensity rescaling of the polarization transport allows one to account implicitly for the volume fraction. This parameter elimination permits a complete exploration, by means of Monte Carlo simulations of the dependence of polarized light transport on microscopic parameters. Analysis of the Mueller matrices obtained from the simulations show that additional correlations (with respect to scalar transport) are obtained between the microscopic parameters and the spatial distribution of specific elements of the Mueller matrix. As a consequence, using carefully chosen polarization states, one can determine an average particle size independently of the volume fraction of particles, with only the knowledge of the refractive-index ratio being required. This analysis is validated with experimental Mueller matrices obtained for emulsions of various size, concentration, and polydispersity.

Phase diagrams of Wyoming Na-montmorillonite clay. Influence of particle anisotropy.

Natural Na-Wyoming montmorillonite was size fractionated by successive centrifugation. Polydisperse particles with average sizes of 400, 290, and 75 nm were then obtained. As the structural charge of the particles belonging to three fractions (determined by cationic exchange capacity measurements) is the same, such a procedure allows studying the effect of particle anisotropy on the colloidal phase behavior of swelling clay particles. Osmotic stress experiments were carried out at different ionic strengths. The osmotic pressure curves display a plateau whose beginning systematically coincides with the sol/gel transition determined by oscillatory stress measurements. The concentration corresponding to the sol/gel transition increases linearly with particle anisotropy, which shows that the sol/gel transition is not directly related to an isotropic/nematic transition of individual clay particles. Indeed, a reverse evolution should be observed for an I/N transition involving the individual clay particles. Still, when observed between crossed polarizer and analyzer, the gel samples exhibit permanent birefringent textures, whereas in the "sol" region, transient birefringence is observed when the samples are sheared. This suggests that interacting clay particles are amenable to generate, at rest and/or under shear, large anisotropic particle associations.