A Comparative Study on the Roll-to-Roll Processing of a Silicate-Polyvinyl Alcohol Composite Barrier Lacquer Using Slot-Die and Reverse Gravure Coating Techniques.

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 cm3 (STP) 1 µmm2 d 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 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 wt% is preferable for the self-metered reverse gravure coating to assure a homogeneously coated layer.

Nanocomposite Coatings Based on Polyvinyl Alcohol and Montmorillonite for High-Barrier Food Packaging.

Materials with high barrier properties against oxygen are required for the packaging of many sensitive foods. Since commodity polymers lack these properties, additional barrier materials are used in plastic-based barrier packaging. These are usually more expensive than commodity polymers and, in higher fractions, also make recycling more difficult. Current developments, therefore, aim at barrier layers that are as thin as possible but retain the barrier properties. One approach is to incorporate nanoparticles into these layers. In this study, the barrier properties of nanocomposite coatings, consisting of unmodified polyvinyl alcohol (PVA), and dispersed stick-shaped halloysite (Hal) or platelet-shaped montmorillonite (MMT) silicate nanoparticles, were investigated. The PVA was dissolved in aqueous nanoparticle dispersions, which were prepared by mechanical shearing, to produce the so-called "nanolacquer." Nanolacquers with nanoparticle concentrations of 7, 30, and 47 vol% with respect to PVA were applied in a single process step with k-bar on a polypropylene substrate film. The integration of 30 vol% platelet-shaped MMT enhances the barrier performance in comparison to pure PVA by a factor of 12 and 17 for oxygen and helium, respectively. Scanning electron microscopy (SEM) shows a homogeneous distribution and a parallel alignment of the nanoparticles within the coated layer. An increase in the crystallinity of PVA was observed due to the nanoparticle integration as demonstrated by x-ray diffraction (XRD) measurements. The investigation by Fourier transform infrared (FTIR) spectroscopy and the activation energy of the permeation coefficient indicate an interaction between the nanoparticles and the PVA. The theoretically calculated values for barrier enhancement accord well with the experimental values, which emphasizes that the gas barrier improvement for oxygen and helium is mainly dominated by the tortuous path effect.

Dispersion and Performance of a Nanoclay/Whey Protein Isolate Coating upon its Upscaling as a Novel Ready-to-Use Formulation for Packaging Converters.

Studies on composition optimisation showed that the mixing of nanoclays to whey protein-isolate (WPI)-based coating formulations offers an effective strategy to reduce the oxygen permeability of coated polymer films. The scaling up of the various processing stages of these formulations was undertaken to prove their industrial feasibility. The aim was to investigate the effect of various preparation methods at different production scales (pilot- and semi-industrial scale) on the barrier performance and morphological properties of the applied nanocomposites. A nano-enhanced composition was converted into a so-called "ready-to-use" formulation by means of a solid-state pre-dispersion process using ball-milling. The process yielded a nearly dust-free, free-flowing powder containing agglomerated particles, which can easily be mixed with water. The preparation of a coating formulation using the ready-to-use granules and its upscaling for roll-to-roll converting at pilot- and semi-industrial scale was also successfully implemented. The effects of both the production at various scales and ultrasound treatment on the morphology and barrier performance of the nanocomposites were characterized by transmission electron microscopy, scanning electron microscopy, as well as oxygen permeability measurements. Results have shown that the addition of nanoclays to WPI-based coating formulations ultimately led to significantly reduced oxygen permeabilities to 0.59 cm3, 100 µm·m-2·d-1·bar-1 (barrier improvement factor, BIF of 5.4) and 0.62 cm3, 100 µm·m-2·d-1·bar-1 (BIF of 5.1) in cases of pilot- and semi-industrial-processed coatings, respectively, compared to a reference without nanoclay. In both cases, a similar degree of nanoparticle orientation was achieved. It was concluded that the solid state pre-dispersion of the nanoplatelets during the production of the ready-to-use formulation is the predominant process determining the ultimate degree of nanoparticle orientation and dispersion state.

Desiccant Films Made of Low-Density Polyethylene with Dispersed Silica Gel-Water Vapor Absorption, Permeability (H2O, N2, O2, CO2), and Mechanical Properties.

Silica gel is a well-known desiccant. Through dispersion of silica gel in a polymer, films can be made that absorb and desorb water vapor. The water vapor absorption becomes reversible by exposing such films to a water vapor pressure below that of the water vapor pressure during absorption, or by heating the film. The intention of this study was to achieve a better understanding about the water vapor absorption, permeability (H2O, N2, O2, CO2), and mechanical properties of films with dispersed silica gel. Low-density polyethylene (PE-LD) monolayer films with a nominal silica gel concentration of 0.2, 0.4, and 0.6 g dispersed silica gel per 1 g film (PE-LD) were prepared and they absorbed up to 0.08 g water vapor per 1 g of film. The water vapor absorption as a function of time was described by using effective diffusion coefficients. The steady state (effective) water vapor permeation coefficients of the films with dispersed silica gel were a factor of 2 to 14 (8.4 to 60.2·10-12 mg·cm·(cm²·s·Pa)-1, 23 °C) higher than for pure PE-LD films (4.3·10-12 mg·cm·(cm²·s·Pa)-1, 23 °C). On the other hand, the steady state gas permeabilities for N2, O2, and CO2 were reduced to around one-third of the pure PE-LD films. An important result is that (effective) water vapor permeation coefficients calculated from results of sorption and measured by permeation experiments yielded similar values. It has been found that it is possible to describe the sorption and diffusion behavior of water by knowing the permeability coefficient and the sorption capacity of the film (Peff.≈Seff.·Deff.). The tensile stress changed only slightly (values between 10 and 14 N mm-²), while the tensile strain at break was reduced with higher nominal silica gel concentration from 318 length-% (pure PE-LD film) to 5 length-% (PE-LD with 0.6 g dispersed silica gel per 1 g film).

A systematic approach for the accurate and rapid measurement of water vapor transmission through ultra-high barrier films.

Flexible organic electronic devices are often protected from degradation by encapsulation in multilayered films with very high barrier properties against moisture and oxygen. However, metrology must be improved to detect such low quantities of permeants. We therefore developed a modified ultra-low permeation measurement device based on a constant-flow carrier-gas system to measure both the transient and stationary water vapor permeation through high-performance barrier films. The accumulation of permeated water vapor before its transport to the detector allows the measurement of very low water vapor transmission rates (WVTRs) down to 2 × 10-5 g m-2 d-1. The measurement cells are stored in a temperature-controlled chamber, allowing WVTR measurements within the temperature range 23-80 °C. Differences in relative humidity can be controlled within the range 15%-90%. The WVTR values determined using the novel measurement device agree with those measured using a commercially available carrier-gas device from MOCON®. Depending on the structure and quality of the barrier film, it may take a long time for the WVTR to reach a steady-state value. However, by using a combination of the time-dependent measurement and the finite element method, we were able to estimate the steady-state WVTR accurately with significantly shorter measurement times.