To prevent greenhouse emissions into the atmosphere, separations like CO2/CH4 and CO2/N2 from natural gas, biogas, and flue gasses are crucial. Polymer membranes gained a key role in gas separations over the past decades, but these polymers are often not organized at a molecular level, which results in a trade-off between permeability and selectivity. In this work, the effect of molecular order and orientation in liquid crystals (LCs) polymer membranes for gas permeation is demonstrated. Using the self-assembly of polymerizable LCs to prepare membranes ensures control over the supramolecular organization and alignment of the building blocks at a molecular level. Robust freestanding LC membranes were fabricated that have various, distinct morphologies (isotropic, nematic cybotactic, and smectic C) and alignment (planar and homeotropic), while using the same chemical composition. Single gas permeation data show that the permeability decreases with increasing molecular order while the ideal gas selectivity of He and CO2 over N2 increases tremendously (36-fold for He/N2 and 21-fold for CO2/N2) when going from randomly ordered to the highly ordered smectic C morphology. The calculated diffusion coefficients showed a 10-fold decrease when going from randomly ordered membranes to ordered smectic C membranes. It is proposed that with increasing molecular order, the free volume elements in the membrane become smaller, which hinders gasses with larger kinetic diameters (Ar, N2) more than gasses with smaller kinetic diameters (He, CO2), inducing selectivity. Comparison of gas sorption and permeation performances of planar and homeotropic aligned smectic C membranes shows the effect of molecular orientation by a 3-fold decrease of the diffusion coefficient of homeotropic aligned smectic C membranes resulting in a diminished gas permeation and increased ideal gas selectivities. These results strongly highlight the importance of molecular order and orientation in LC polymer membranes for gas separation.
23 September 2022 in ACS Applied Polymer Materials
For preserving food packed in environmentally friendly and recyclable paperboard packages, it is important to have sufficient gas barrier performance of the paperboard container. Paperboard has poor intrinsic barrier properties and to overcome this deficiency, so a barrier coating is needed that does not hinder the recycling of the paperboard substrate. However, the gas barrier properties and the recyclability of such coatings have been rarely studied. Here, both the gas barrier performance and the removal of an alkali-soluble resin (ASR)-stabilized waterborne barrier coatings from paperboard are investigated. For barriers for gases, such as nitrogen, carbon dioxide, and oxygen, defect-free coatings are needed which is achieved by applying three coating layers. The oxygen transmission rate (OTR) of the three-layered coating on paperboard was 920 cm3/(m2∙day). For water vapor barriers, two coating layers already show a strong improvement, as water follows a different penetration mechanism than the other tested gases. The water vapor transmission rate WVTR of double coated paperboard was 240 g/(m2∙day). Preliminary results show that the coating is removed by immersion of the coated paperboard in an aqueous alkaline solution at room temperature. This causes de-protonation of the carboxylic acids of the ASR and subsequent re-dispersion of the coating in water. Removing double-layer coatings from the paperboard is more challenging, possibly due to the coating/coating interface between the two coating layers and enhanced adhesion between coating and paperboard.