Restructuring of colloidal cakes during dewatering.

Aqueous suspensions of aggregated silica particles have been dewatered to the point where the colloidal aggregates connect to each other and build a macroscopic network. These wet cakes have been compressed through the application of osmotic pressure. Some cakes offer a strong resistance to osmotic pressure and remain at a low volume fraction of solids; other cakes yield at low applied pressures, achieving nearly complete solid/liquid separation. We used small angle neutron scattering and transmission electron microscopy to determine the processes by which the particles move and reorganize during cake collapse. We found that these restructuring processes follow a general course composed of three stages: (1) at all scales, voids are compressed, with large voids compressed more extensively than smaller ones; the local order remains unchanged; (2) all voids with diameters in the range of 2-20 particle diameters collapse, and a few dense regions (lumps) are formed; and (3) the dense lumps build a rigid skeleton that resists further compression. Depending on the nature of interparticle bonds, some cakes jump spontaneously into stage 3 while others remain stuck in stage 1. To elucidate the relation between bond strength and compression resistance, we have constructed a numerical model of the colloidal network. In this model, particles interact through noncentral forces that are produced by springs attached to their surfaces. Networks made of bonds that break upon stretching evolve through a plastic deformation that reproduces the three stages of restructuring evidenced by the experiments. Networks made of bonds that are fragile jump into stage 3. Networks made of bonds that can be stretched without breaking evolve through elastic compression and restructure only according to stage 1.

Cholesteric liquid crystals with a helical pitch gradient: spatial distribution of the concentration of chiral groups by Raman mapping in relation with the optical response and the microstructure.

Cholesteric liquid crystals (CLC) selectively reflect light when the helical pitch is of the order of the wavelength of the incident beam propagating along the helix axis. The wavelength bandwidth, related to the optical anisotropy, is typically limited to a few tens of nanometers in the visible part of the spectrum, which is insufficient for applications such as white-or-black polarizer-free reflective displays and smart windows for the control of the solar light and heat. A way to make cholesteric films reflecting in a broad wavelength band consists in associating various cholesteric pitches in the same film. In this work, it is shown how a study by confocal micro Raman spectrometry mapping makes it possible to have access to information accounting for the local organization of CLCs in the case of graded pitch materials. These investigations will be correlated to the optical response and the transverse microstructure of the CLC material as investigated by transmission electron microscopy. An accurate analysis of the vibrational behavior evolution of the C==O can be correlated to the evolution of the populations of the chiral and achiral groups in the case of the interdiffusion of two CLC substances with various stoechiometries. Besides an easy measurement of the Raman spectrum gives the opportunity to quantify the relative ratio of the mesogenic species and thus to go up by a simple way to the pitch of the helical structure.

Glassy cholesteric structure: thickness variation induced by electron radiation in transmission electron microscopy investigated by atomic force microscopy.

During the observation of glassy cholesteric liquid crystals in transmission electron microscopy (TEM), a new contrast is created or enhanced by electron radiation which has a direct relationship with the periodic microstructure of the specimen. In this paper, we investigate the variations of the sample thickness and mass density as possible causes of this irradiation contrast. By means of observations in atomic force microscopy (AFM) coupled to TEM, we compared the surface corrugations of non-irradiated and irradiated specimens. It is shown that the final contrast is the result of several processes. including fracture during ultramicrotomy and mass loss during irradiation. Mass loss acts as an etching, and hence results in a decrease of the sample thickness. The etching depends on the initial molecular orientation, thus evidencing the latent structure. An electron channelling mechanism is suggested to explain this behaviour.