Flexible optoelectronic packaging is required to provide an ultrahigh barrier to oxygen under ambient conditions, meaning at a relative humidity above 50%. Many polymeric packaging materials, however, adsorb water vapor and the consequential softening is detrimental for the barrier properties. Despite its importance, systematic studies on the impact of the relative humidity (RH) on the oxygen permeability (OP) of clay nanocomposite barriers and convincing evidence for a potential hydrophobization due to compounding with nanosheets are scarce. Especially at filler contents greater than 30 vol %, as required for ultrahigh barriers, a severe confinement is imposed on interlayered polymer and thus its permeability properties are expected to be significantly modified as compared to the bulk. A systematic study of the relation between permeability and RH requires nanocomposite films that differ in filler content but at the same time are comparable with respect to aspect ratio, filler type, quality of texture, and one-dimensional crystallinity. By applying water-soluble polyvinylpyrrolidone (PVP) and ultrahigh-aspect-ratio synthetic clay (sodium fluorohectorite), we were able to prepare hybrid samples that meet these requirements for the first time. By spray coating, the components self-assemble into hybrid films of one-dimensional crystalline Bragg stacks. Two such hybrid films with filler contents of 31 and 40 vol % were fabricated. Indeed, the filler content was found to greatly affect the dependence of the oxygen permeability on RH. Comparing the performance of these two films, the OP in the 40 vol % sample was four times lower than would be expected because of the increase in filler content. To the best of our knowledge, this is the first convincing evidence for a pronounced confinement effect on the permeability.
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).
When suspensions are exposed to shear forces, the particles may form ordered structures depending on their shapes, concentrations, and the material. For some processes, e.g., for wet-film coating, it is important to know how fast these structures form in shear fields and for how long the structures persist when the shear is relaxed. To obtain information on the particle structure formation and the decay time, the effective viscosity of nematic suspensions of Na-hectorite nanosheets was investigated by rheology employing a cone-plate measurement geometry. The necessary time for the formation textured nematic films could be deduced by carrying out effective viscosity measurements at constant time steps. Information could also be obtained on the lifetime of the platelet textures when shear is relaxed. All this information was employed to identify geometrical requirements for slot dies to produce barrier liners with nanosheet layers oriented parallel to PET substrates. Thereby, we obtained green and simple coatings that are in line with state-of-the-art high-performance materials such as metalized plastic foils in terms of oxygen barrier properties.
Conventional biodegradable polymers such as poly(lactic acid) (PLA) are an attractive alternative to replace traditional nondegradable food packaging films which plague the environment. However, PLA has shown to not be degradable in some environmentally relevant conditions, including within the freshwater systems. Additionally, PLA suffers from very poor barrier properties, which could result in food spoilage. Compositing with clay has been used to improve barrier properties according to tortuous path theory. Here a synthetic, large aspect ratio Na-Hectorite is used that may be utterly delaminated in an organic solvent and composited with PLA by modification with 18-crown-6 (18C6Hec), yielding a castable, homogeneous nematic suspension. Upon drying, thermodynamics drive the suspension toward segregation into sublayers of PLA and partially restacked 18C6Hec in situ. This unique self-assembled nanostructure combines the best of two worlds: The aspect ratio remains high and results in a 99.3% reduction in oxygen permeability. Additionally, the film shows surprisingly high resistance to swelling at elevated humidity, but once soaked in water, clay swelling is triggered, which fragments the film and drastically increases the surface area by 2500%. Accelerated degradation is observed under controlled enzymatic conditions and in an environmentally relevant wastewater medium during CO 2 evolution testing.
Cellulose acetate (CA) was partially acrylated, and the resulting cellulose acetate acrylate (acryl-substitution degree of 0.2) underwent quantitative thio-Michael click reactions with various thiols. A toolbox of functional CA polymers was obtained in this way, and their properties were studied. The modification with fatty alkyl thiols led to hydrophobic materials with large water drop contact angles. Octadecylthio-, butoxycarbonylpropylthio-, and furanylthio-modifications formed highly transparent materials. The new derivative CAASFur disintegrated completely under industrial composting conditions. Films of modified CA polymers were cast and investigated in terms of barrier properties. The nanocomposite of CAAS18 compounded with a synthetic layered silicate (hectorite) of a large aspect ratio showed permeabilities as low as 0.09 g mm m −2 day −1 for water vapor and 0.16 cm 3 mm m −2 day −1 atm −1 for oxygen. This portfolio of functional CA polymers opens the door to new applications.
Expensive biodegradable packaging as a preventative measure against continued accumulation of plastic waste in our environment is often in conflict with the need for high performing packaging materials that prevent...
The goal of reconciling all packaging requirements, e.g., mechanical resistance, transparency, flexibility, and gas barrier properties, is immensely challenging for packaging materials. Particularly, the combination of flexibility and good gas barrier properties poses a serious problem, especially when barrier requirements can only be met by lamination with a metal foil, metalization, or vapor-deposited ceramic layers, as all of these tend to be nonstretchable. In this work, we produced a stretchable nanocomposite barrier composed of onedimensional (1D) crystalline (Bragg stack) barrier films composed of alternating layers of poly(ethylene glycol) (PEG) and synthetic sodium fluorohectorite (Hec) nanosheets. By sandwiching the Bragg stack type film between two plasticized poly(vinyl alcohol) (PVOH) layers, a waterborne laminate was obtained that outperforms commercial polymer materials in terms of water vapor permeability (WVP = 2.8 g mm m −2 day −1 bar −1 at 23 °C and 85% relative humidity), which is remarkable for an entirely water-soluble film. Moreover, no deterioration of barrier performance up to 10% elongation was observed, rendering the transparent self-standing laminate promising for thermoformed blister packaging, shrink wrap, or vacuum packaging. Besides the low WVP, the scalable and green processing method makes this technology auspicious for real-world applications.
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