Textured kaolinite and halloysite-based materials were shaped by tape casting in order to promote the alignment of clay particles along the tape casting direction and to investigate the structure evolution of these phyllosilicates during the dehydroxylation process. The crystallinity indexes HI and R2 of the starting kaolins (KRG and KCS) were determined and appeared close to values found for the well-ordered reference kaolin KGa-1b. The halloysite clay exhibited trimodal grain size distribution and tended to be less textured than KRG and KCS according to the (002) pole figures performed on green tapes. The constant heating rate derived kinetic parameters matched the expected range. We followed the dehydroxylation of kaolinite and halloysite through in situ high-temperature X-ray diffraction measurements at the ESRF synchrotron radiation source on the D2AM beamline. The dehydroxylation of these kaolinite and halloysite occurred between 425 °C and 675 °C for KRG and KCS and from 500 °C to 650 °C for halloysite. In addition, the evolution of the basal distance of kaolinite regarding the heat treatment temperature confirmed that the dehydroxylation process occurred in three steps: delamination, dehydroxylation, and formation of metakaolinite. The calculated coefficient of thermal expansion (CTE) along the c axe values were close to 17 × 10−6 °C−1 for kaolinite (KCS and KRG) and 14 × 10−6 °C−1 for halloysite.
The present study aimed at investigating the influence of the concentration of sodium silicate and sodium hexametaphosphate on the dispersion of an aqueous kaolinitic clay slurry regarding further use for the tape casting process. The zeta potential of the kaolinitic clay slurry matched the requirements for tape casting. The addition of magnesite in the kaolinitic slurries tended to increase the zeta potential towards the required limit values. Despite this, the further addition of surfactants allowed improving the zeta potential in agreement with the tape casting conditions. Accordingly, the rheological behavior, under continuous and oscillatory flow conditions, of various mixtures of magnesite and a kaolinitic clay was studied. Regarding the pH and the zeta potential measurements, the E–F attraction prevailed at low pH value, and F–F or E–E attraction was predominant at high pH value. All slurries exhibited a shear thinning behavior, which was well-correlated by the Herschel–Bulkley model. It appeared that the best stability for the kaolinitic clay slurries was obtained while using 0.4 mass% and 1.2 mass% of sodium hexametaphosphate and sodium silicate, respectively. An increase in the magnesite concentration above 6 mass% led to a complex behavior with low cohesion energy due to the occurrence of soluble complexes.
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