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.

In recent decades, talc and kaolinite have been widely used as raw materials for the ceramic industry. In this study, the final characteristics of kaolinitic clay mixed with 6 mass% of magnesite obtained in our previous work were compared with those obtained with mixtures of kaolin (kaolin BIP) and talc (as the source of magnesium oxide). However, different amounts of talc in the kaolin powder were studied, namely 10, 30, and 50 mass% of added talc (with respect to kaolin + talc). The tape casting process was used during this work in order to manufacture the green tapes in an aqueous system with 0.2 mass% of dispersant. Subsequently, the green tapes were heated to 1000 and 1100 °C with a dwelling time of 12 min. The green and sintering tapes were characterized using the following techniques: DTA/TG, X-ray diffraction, porosity, and flexural strength analyses. The results obtained from our previous work indicate that the specimen with 6 mass% of MgCO₃ sintered at 1200 °C for 3 h exhibited the best performances, with high flexural strength and weak porosity value—117 MPa and 27%—respectively. As results from this study, the optimal mechanical and thermal properties of sintering tapes were obtained for the specimen with 10 mass% of added talc sintered at 1100 °C. Indeed, this specimen exhibited 50 MPa and 43% of stress to rupture and apparent porosity, respectively.

Halloysite and kaolinite are dioctahedral TO phyllosilicates that drive the interest of scientists for formulating environmental friendly materials, and consequently in the field of ceramics. The main scope of this study was the understanding of the texture evolution upon the dehydroxylation reaction and the influence of the presence of halloysite. In situ synchrotron (002) and (111) poles figures were recorded on the DiffAbs beamline at SOLEIL Synchrotron, from room temperature to 1000°C, on kaolinite and/or halloysite-rich samples shaped by tape casting. Commercial kaolins and halloysite provided by Imerys company were used. The samples were labeled KRG100, KCS100, H100, KRG50H50 and KRG59H50 in relation with the wt. % of kaolin (KRG, KCS) or halloysite (H) clays. In samples KCS100 and KRG100, a strong texture was observed until in situ annealing at 700°C, with respect to the c-axis of kaolinite. One the contrary, the texture with respect to the c-axis of halloysite for the sample H100 was weak whatever the temperature was. Moreover, this weak texture disappeared before the complete dehydroxylation of halloysite. This is due to the opening of some halloysite tubes. When considering the samples KRG50H50 and KCS50H50, a significant texture was observed with the c-axis preferentially oriented perpendicular to the sample surface . The presence of kaolinite platelets predominated onto the alignment of halloysites tubes. Furthermore, it was noted that the halloysite influenced the (002) diffracted intensity into the temperature range 20 °C and 400 °C. Above 400°C, the behavior obtained for the (002) reflection in samples KRG50H50 and KCS50H50 was similar to the behavior noticed for pure kaolins KRG100 and KCS100 respectively. The dehydroxylation temperature range appeared to be relevant with combined effect of kaolinite and halloysite transformations arising from KRG100 or KCS100 and H100 samples. Therefore, the onset point of dehydroxylation is 550 °C ± 25 °C for KRG100, KCS100 KRG50H50 and KCS50H50. For the pure halloysite H100 sample, the dehydroxylation starts at lower temperature 475°C. It was also noted that during the dehydroxylation of kaolinite, the characteristic portion of ring related to the diffracted intensity of the (111) reflection located at χ = 45 ° tended to disappear above 550 °C and led to the formation of a new transitory phase with a (111) reflection with perpendicular alignment to the c-axis. Indeed, an epitaxial relationship with the (111) kaolinite reflection could be assumed. Further X-ray scattering experiments allowed highlighting the effective offset temperature of the dehydroxylation, which was identified as close to 720 °C. The metakaolinite obtained undergone structural transformation to another transitory phase at 1000°C.