This article demonstrates the occurrence of a true isotropic͞nematic 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 strength͞volume 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 sol͞gel transition hinders the isotropic͞ 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.colloids ͉ liquid crystal ͉ phase transitions S welling clay minerals are layered compounds that bear a negative layer charge compensated by interlayer exchangeable cations whose valence and hydration properties control both swelling and colloidal behavior. One of the most important properties of swelling clay minerals is their ability to form yield stress materials when dispersed in water. This feature, extensively used in various industrial applications (drilling fluids, food industry, cosmetic industry, etc.), also plays a major role in many fundamental processes occurring at the Earth's surface, such as slipping processes in plate-boundary faults (1-4) or landslide triggering (5-9). For these reasons, numerous studies have focused on the rheology of aqueous clay suspensions with particular emphasis on yield stress, thixotropy, and aging (10-15). However, most studies neglect a key feature of clay minerals, i.e., their anisotropic shape. Actually, due to their high aspect ratio typically ranging between 25 and 1,000, these materials should very likely form liquid-crystalline phases (16), such as those observed for rod-like clay particles, such as imogolite in aqueous media (17), or organophilic sepiolite clay particles in nonaqueous solvents (18). A phase transition was indeed observed by Langmuir (19, ** ) as early as 1938 in suspensions of natural hectorite swelling clay. However, all subsequent studies failed to reproduce this crucial observation and give evidence of a clear thermodynamic liquid-crystalline order but instead revealed a dominant gel formation (20). Such behavior is observed for both highly polydisperse natural samples (21) and synthetic monodisperse ones (22). The structure and formation mechanisms of the gel are still under debate. Indeed, although some of the gel features indicate nematic ordering (23,24)...
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.
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.
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.
The phase behaviour of aqueous suspensions of NAu1 nontronite was studied on size-selected particles by combining osmotic pressure measurements, visual observations under polarized light, rheological experiments and Small Angle X-ray Scattering (SAXS). NAu1 suspensions display a liquid crystalline behaviour as they exhibit a Isotropic/Nematic (I/N) transition that occurs before the sol/gel transition for ionic strengths below 10–3 M/L. This I/N transition shifts towards 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. In the gel phase a local lamellar order is observed which shows that the “house of cards” model is not appropriate for describing the gel structure in swelling clay materials at low ionic strength. Furthermore, 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 repulsion between charged infinite parallel planes. In terms of rheological properties, even if the thermodynamical status of the sol/gel transition remains partially unclear, 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 modelling of the flow curves shows that for all the particles an approach based on excluded volume effects captures most features of nontronite suspensions.
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