Onset of Osmotic Swelling in Highly Charged Clay Minerals.

Delamination by osmotic swelling of layered materials is generally thought to become increasingly difficult, if not impossible, with increasing layer charge density because of strong Coulomb interactions. Nevertheless, for the class of 2:1 layered silicates, very few examples of delaminating organo-vermiculites were reported in literature. We propose a mechanism for this repulsive osmotic swelling of highly charged vermiculites based on repulsive counterion translational entropy that dominates the interaction of adjacent layers above a certain threshold separation. Based on this mechanistic insight, we were able to identify several organic interlayer cations appropriate to delaminate highly charged, vermiculite-type clay minerals. These findings suggest that the osmotic swelling of highly charged organoclays is a generally applicable phenomenon rather than the odd exemption.

Disorder-Order Transition-Improving the Moisture Sensitivity of Waterborne Nanocomposite Barriers.

Systematic studies on the influence of crystalline vs disordered nanocomposite structures on barrier properties and water vapor sensitivity are scarce as it is difficult to switch between the two morphologies without changing other critical parameters. By combining water-soluble poly(vinyl alcohol) (PVOH) and ultrahigh aspect ratio synthetic sodium fluorohectorite (Hec) as filler, we were able to fabricate nanocomposites from a single nematic aqueous suspension by slot die coating that, depending on the drying temperature, forms different desired morphologies. Increasing the drying temperature from 20 to 50 °C for the same formulation triggers phase segregation and disordered nanocomposites are obtained, while at room temperature, one-dimensional (1D) crystalline, intercalated hybrid Bragg Stacks form. The onset of swelling of the crystalline morphology is pushed to significantly higher relative humidity (RH). This disorder-order transition renders PVOH/Hec a promising barrier material at RH of up to 65%, which is relevant for food packaging. The oxygen permeability (OP) of the 1D crystalline PVOH/Hec is an order of magnitude lower compared to the OP of the disordered nanocomposite at this elevated RH (OP = 0.007 cm3 µm m-2 day-1 bar-1 cf. OP = 0.047 cm3 µm m-2 day-1 bar-1 at 23 °C and 65% RH).

Layering-Triggered Delayering with Exfoliated High-Aspect Ratio Layered Silicate for Enhanced Gas Barrier, Mechanical Properties, and Degradability of Biodegradable Polymers.

Research on biodegradable polymers with the intention of fast, complete degradation in industrial compost (i-compost) for organic recyclability is paramount to identifying solutions to the problem of excessive plastic waste originating specifically from packaging. Conventional biodegradable polymers, such as polylactide (PLA), are far from optimum for this application due to the poor gas barrier properties and slow degradation. In the paper, a new concept (triggered degradation by delayering) is shown in which exfoliated, self-assembled sodium-hectorite (Hec) arranged in a layer-by-layer manner alternating with electrospun hot-pressed PLA provides strong gas barrier properties at high humidity and simultaneously accelerates the degradation of PLA, as tested in an enzymatic solution and i-compost. A thin composite film (thickness 56 µm) shows a tensile strength and modulus 58 and 2000 MPa, respectively, whereas oxygen permeability is as low as 0.0064 cm3 cm m-2 day-1 bar-1. Furthermore, the delayering of the composite film by swelling of Hec layer led to accelerated degradation of PLA, as shown in detail by enzymatic and compost degradation. Since such concepts for enhanced degradability are urgently needed for sustainable utilization of biodegradable polymers in plastic waste management, the present work is an important step ahead.

Lightweight Ultra-High-Barrier Liners for Helium and Hydrogen.

Upcoming efficient air-borne wind energy concepts and communication technologies applying lighter-than-air platforms require high-performance barrier coatings, which concomitantly and nonselectively block permeation not only of helium but also of ozone and water vapor. Similarly, with the emergence of green hydrogen economy, lightweight barrier materials for storage and transport of this highly diffusive gas are very much sought-after, particularly in aviation technology. Here the fabrication of ultraperformance nanocomposite barrier liners by spray coating lamellar liquid crystalline dispersions of high aspect ratio (∼20 000) silicate nanosheets mixed with poly(vinyl alcohol) on a PET substrate foil is presented. Lightweight nanocomposite liners with 50 wt % filler content are obtained showing helium and hydrogen permeabilities as low as 0.8 and 0.6 cm3 µm m-2 day-1 atm-1, respectively. This exhibits an improvement up to a factor of 4 × 103 as compared to high-barrier polymers such as ethylene vinyl alcohol copolymers. Furthermore, ozone resistance, illustrated by oxygen permeability measurements at elevated relative humidity (75% r.h.), and water vapor resistance are demonstrated. Moreover, the technically benign processing by spray coating will render this barrier technology easily transferable to real lighter-than-air technologies or irregular- and concave-shaped hydrogen tanks.

Structural Insights into Water-Based Spider Silk Protein-Nanoclay Composites with Excellent Gas and Water Vapor Barrier Properties.

Nature reveals a great variety of inorganic-organic composite materials exhibiting good mechanical properties, high thermal and chemical stability, and good barrier properties. One class of natural bio-nanocomposites, e.g. found in mussel shells, comprises protein matrices with layered inorganic fillers. Inspired by such natural bio-nanocomposites, the cationic recombinant spider silk protein eADF4(κ16) was processed together with the synthetic layered silicate sodium hectorite in an all-aqueous setup. Drop-casting of this bio-nanocomposite resulted in a thermally and chemically stable film reflecting a one-dimensional crystal. Surprisingly, this bio-nanocomposite coating was, though produced in an all-aqueous process, completely water insoluble. Analyzing the structural details showed a low inner free volume due to the well-oriented self-assembly/alignment of the spider silk proteins on the nanoclay surface, yielding high oxygen and water vapor barrier properties. The here demonstrated properties in combination with good biocompatibility qualify this new bio-nanocomposite to be used in packaging applications.