The integration of platelet-shaped montmorillonite particles to improve the oxygen barrier of polyvinyl-alcohol-based barrier layers is state-of-the-art, but research on roll-to-roll coatings of such composite barrier lacquers has not been widely published. In this study, two different coating techniques, slot-die and reverse gravure, were used on a roll-to-roll scale to apply barrier lacquers comprising polyvinyl alcohol and montmorillonite. The lacquers were analyzed regarding viscosity at certain shear rates and surface energy and the dried coating layers regarding oxygen barrier, surface morphology, and particle orientation. Low permeability coefficients delivering a high oxygen barrier of 0.14 and 0.12 $\frac{{\mathrm{cm}}^3\left(\mathrm{STP}\right)1\mathsf{\mu }\mathrm{m}}{{\mathrm{m}}^2\mathrm{d}\mathrm{bar}}$ were achieved for the coating layers with slot-die and reverse gravure coating, respectively. It turned out that the properties of the barrier lacquer need to be adjusted to the coating technique to achieve high oxygen barrier performance. By tailoring the barrier lacquer formulation, the orientation of the platelet-shaped montmorillonite particles can be achieved using both techniques. A low solid content of down to 3$\mathrm{wt}\%$ is preferable for the premetered slot-die coating, because it results in low agglomeration quantity in the coating layer. A high solid content of up to 9$\mathrm{wt}\%$ is preferable for the self-metered reverse gravure coating to assure a homogeneously coated layer.

The motivations of the present work are to investigate the exfoliation of montmorillonite within a linear low-density polyethylene matrix and to control its orientation during the cast extrusion process. The first part is focused on the exfoliation of the montmorillonite through the melt extrusion process. The accuracy and relevance of each method used to determine the exfoliation state of montmorillonite have been examined, thanks to X-ray diffraction, transmission electronic microscopy, and rheology. All these methods have presented limitations, but the combination of all leads to a better estimation of the exfoliation state. Finally, the orientation of the montmorillonite is quantified systematically by X-ray texture analysis and correlated with process parameters to discern which one is affecting their orientation. The results have demonstrated an enhancement of the “in-plane” orientation of the montmorillonite with the exfoliation, especially at high concentration and when combined with cast extrusion. Finally, in the multi-nano-layer polymer film configuration, the reduction of the individual layers 29 nm thickness leads to some orientation improvements. However, these improvements are almost at the same level as the concentration effect in a monolayer system. This work gives an overview of all the parameters needed to achieve a significant organo-modified montmorillonite “in-plane” orientation.