Henrik Hemmen

Intercalation and Retention of Carbon Dioxide in a Smectite Clay promoted by Interlayer Cations

A good material for CO2 capture should possess some specific properties: (i) a large effective surface area with good adsorption capacity, (ii) selectivity for CO2, (iii) regeneration capacity with minimum energy input, allowing reutilization of the material for CO2 adsorption, and (iv) low cost and high environmental friendliness. Smectite clays are layered nanoporous materials that may be good candidates in this context. Here we report experiments which show that gaseous CO2 intercalates into the interlayer nano-space of smectite clay (synthetic fluorohectorite) at conditions close to ambient. The rate of intercalation, as well as the retention ability of CO2 was found to be strongly dependent on the type of the interlayer cation, which in the present case is Li+, Na+ or Ni2+. Interestingly, we observe that the smectite Li-fluorohectorite is able to retain CO2 up to a temperature of 35°C at ambient pressure, and that the captured CO2 can be released by heating above this temperature. Our estimates indicate that smectite clays, even with the standard cations analyzed here, can capture an amount of CO2 comparable to other materials studied in this context.

The isotropic-nematic interface in suspensions of Na-fluorohectorite synthetic clay.

Colloidal suspensions of Na-fluorohectorite synthetic clay platelets in saline water exhibit coexisting isotropic and nematic phases, due to gravitational separation of the polydisperse particles. We study the ordering of the platelets at the interfaces between various coexisting phases. Four different experimental techniques are employed: visual observation of birefringence, synchrotron wide angle and small-angle X-ray scattering, and magnetic resonance imaging. We find that at the narrow isotropic sol-nematic sol interface the platelets are lying horizontally, i.e. with their mean platelet normal along the vertical direction. The experiments indicate that the platelets align homeotropically both at the isotropic sol-nematic sol interface and at the nematic sol-wall interface. We further investigate the complex alignment effect of a horizontally applied magnetic field in the nematic sol, and we compare it with the adjacent nematic gel.

Swelling transition of a clay induced by heating.

Clays are of paramount importance for soil stability, but also in applications ranging from oil recovery to composites and hydrogels. Generically, clays are divided into two subclasses: macroscopically swelling, ‘active’ clays that have the capacity for taking up large amounts of water to form stable gels, and ‘passive’ or non-swelling clays; the former stabilize soils whereas the latter are known to lead to landslides. However, it has been unclear so far what mechanisms underlie clay swelling. Here, we report the first observation of a temperature-induced transition from a passive to an active, swelling clay. We propose a simple description of the swelling transition; while net attractive interactions are dominant at low temperatures so that the clay particles remain attached to each other in stacks, at higher temperatures it is energetically favourable for the clay to swell due to the entropy that is gained by counterions which are liberated during swelling.

X-ray Studies of Carbon Dioxide Intercalation in Na-Fluorohectorite Clay at Near-Ambient Conditions

We show experimentally that gaseous CO(2) intercalates into the interlayer space of the synthetic smectite clay Na-fluorohectorite at conditions not too far from ambient. The mean interlayer repetition distance of the clay when CO(2) is intercalated is found to be 12.5 Å for the conditions -20 °C and 15 bar. The magnitude of the expansion of the interlayer upon intercalation is indistinguishable from that observed in the dehydrated-monohydrated transition for H(2)O, but the possibility of water intercalation is ruled out by a careful analysis of the experimental conditions and repeating the measurements exposing the clay to nitrogen gas. The dynamics of the process is observed to be dependent on the pressure, with a higher intercalation rate at increased pressure. The rate of CO(2) intercalation at the studied conditions is found to be several orders of magnitude slower than the intercalation rate of water or humidity at ambient pressure and temperature.

Mueller matrix imaging of nematic textures in colloidal dispersions of Na-fluorohectorite synthetic clay

A Mueller Matrix Imaging Ellipsometer system is operated in transmission and used to study nematic textures in colloidal dispersions of synthetic Na-fluorohectorite clay platelets in solution. It is clearly observed that the anisometric particles organize into phases with strong birefringence, which results in a strong retardance. The Mueller matrix imaging technique supplies an image of the retardance matrix, even in the presence of other effects such as light scattering and diattenuation. The spatial variation of the absolute value of the retardance, the orientation of the fast axis of the retardance, the total diattenuation and the orientation of the diattenuation are presented. In particular, from knowledge of the anisotropic shape of the particles, the orientation of the particles within ordered domains, and the density of the particles within the domains are spatially determined. The experiments are based on adding synthetic clay particles into a solution contained in a thin rectangular glass container. Upon letting gravitation act on the sample, different phases appear after a few weeks. One phase contains nematic textures and we are able to determine the ordering and also estimate the density of the domains/texture within the phase, in addition to estimating the local order within a domain with an image resolution of 12 μm.