For the last decades, nanocomposites materials have been widely studied in the scientific literature as they provide substantial properties enhancements, even at low nanoparticles content. Their performance depends on a number of parameters but the nanoparticles dispersion and distribution state remains the key challenge in order to obtain the full nanocomposites’ potential in terms of, e.g., flame retardance, mechanical, barrier and thermal properties, etc., that would allow extending their use in the industry. While the amount of existing research and indeed review papers regarding the formulation of nanocomposites is already significant, after listing the most common applications, this review focuses more in-depth on the properties and materials of relevance in three target sectors: packaging, solar energy and automotive. In terms of advances in the processing of nanocomposites, this review discusses various enhancement technologies such as the use of ultrasounds for in-process nanoparticles dispersion. In the case of nanocoatings, it describes the different conventionally used processes as well as nanoparticles deposition by electro-hydrodynamic processing. All in all, this review gives the basics both in terms of composition and of processing aspects to reach optimal properties for using nanocomposites in the selected applications. As an outlook, up-to-date nanosafety issues are discussed.
The aim of this study was to analyze how corona dosages above recommended levels affect film surface energy and hydrophobic recovery of such treated film surfaces as well as laminate bond strength of laminates made of these films. The adhesive for lamination was a polyurethane‐adhesive with a dry film thickness of ∼5 µm. Polar and dispersive parts of the surface energy were measured frequently according to DIN 55660‐2 (Owens–Wendt–Rabel‐and‐Kaelble method) for up to 140 days after corona treatment. The corona dosage had a value of up to 280 W min/m2. Laminate bond strength was measured according to DIN 55543‐5. The effect of corona treatment was highest for low‐density polyethylene (PE‐LD) films, mean for biaxial‐oriented polypropylene (PP‐BO) films, and lowest for biaxial‐oriented poly(ethylene terephthalate) (PET‐BO) films. With increasing storage time, surface energy decreased, as expected. The higher the effect of corona treatment, the faster the polar part of surface energy decreased. At PE‐LD, laminate bond strength increased with a higher corona dosage from 0.05 to 8.87 mN/15 mm, whereas at PET‐BO and PP‐BO laminate bond strength was so high that samples teared before delamination during bond strength testing. By our results is shown that corona dosages above recommended levels resulted in higher laminate bond strength. Only at PP‐BO a reduction of laminate bond strength due to “overtreatment” was be observed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45842.
In this study, the effects of the addition of montmorillonite (MMT) nanoplatelets on whey protein isolate (WPI)-based nanocomposite films and coatings were investigated. The main objective was the development of WPI-based MMT nanocomposites with enhanced barrier and mechanical properties. WPI-based nanocomposite cast films and coatings were prepared by dispersing 0% (reference sample), 3, 6, 9% (w/w protein) MMT, or, depending on the protein concentration, also 12 and 15% (w/w protein) MMT into native WPI-based dispersions, followed by subsequent denaturation during the drying and curing process. The natural MMT nanofillers could be randomly dispersed into film-forming WPI-based nanodispersions, displaying good compatibility with the hydrophilic biopolymer matrix. As a result, by addition of 15% (w/w protein) MMT into 10% (w/w dispersion) WPI-based cast films or coatings, the oxygen permeability (OP) was reduced by 91% for glycerol-plasticized and 84% for sorbitol-plasticized coatings, water vapor transmission rate was reduced by 58% for sorbitol-plasticized cast films. Due to the addition of MMT nanofillers, the Young's modulus and tensile strength improved by 315 and 129%, respectively, whereas elongation at break declined by 77% for glycerol-plasticized cast films. In addition, comparison of plasticizer type revealed that sorbitol-plasticized cast films were generally stiffer and stronger, but less flexible compared glycerol-plasticized cast films. Viscosity measurements demonstrated good processability and suitability for up-scaled industrial processes of native WPI-based nanocomposite dispersions, even at high-nanofiller loadings. These results suggest that the addition of natural MMT nanofillers into native WPI-based matrices to form nanocomposite films and coatings holds great potential to replace well-established, fossil-based packaging materials for at least certain applications such as oxygen barriers as part of multilayer flexible packaging films.
Whey protein based films have received considerable attention to be used for environment friendly packaging applications. However, such biopolymers are prevented for use in commercial packaging due to their limited mechanical and barrier performance. The addition of nanofillers is a common method to overcome those drawbacks of biopolymers. Whey protein isolate (WPI) based nanocomposite cast films and coatings were produced using montmorillonite and vermiculite clay as nanofiller in different concentrations. Uniform distribution of filler within the polymeric matrix was confirmed by scanning electron microscopy. Mechanical properties such as tensile strength as well as Young's modulus were increased after increasing the filler content, while elongation at break values decreased. All samples showed weak barrier potential against water vapor. Nanoclay incorporation, however, reduced water vapor transmission rates by approximately 50%. The oxygen barrier performance was improved for all nanocomposites. Results also indicated proportionality with the filler ratio according to applied models. The highest barrier improvement factors (BIF) were greater than five for the cast films and even greater than sixteen for the coatings. Developed WPIbased composites depicted nanoenhanced material properties representing a promising alternative to fossil-based packaging films.
Metallized films consisting of thin, vacuum-deposited inorganic layers are used for a wide range of packaging applications for foods, pharmaceuticals and other technical purposes. They are made as laminates and consist of a polymeric film (substrate), an inorganic layer, mostly aluminum (Al), and a top layer, laminated to the inorganic layer using a suitable adhesive. One major quality indicator in such flexible packaging materials is the adhesion strength between the inorganic layer and the substrate. In order to measure the adhesion strength of thin Al layers deposited on a substrate, the following procedure is often used: Ethylene acrylic acid (EAA)-films are thermally sealed to the Al layers. In a subsequent peel test, the EAA-film is peeled-off at 180 • peel angle, delaminating the Al layer from the substrate. This method shows weaknesses in cases of high bond strength: The sealed EAA-film is elongated or even torn during the measurements, whereby it is difficult to obtain reproducible and repeatable results. In this study two alternative approaches have been tested to overcome the weaknesses of EAA-peel test. One of them is to use thermally sealable polymeric films, such as amorphous poly(ethylene terephthalate) and amorphous polyamide (both having a high mechanical strength), instead of the EAA film. Although the adhesion forces might have been weakened during the heat lamination of these selected films onto the Al surface, a quantitative comparison between the three different types of metallized films (with low, medium and high adhesion strength) is found to be promising by this approach. The other approach is to perform the peel tests with the laminates of the metallized films. The laminates are produced by laminating a low density polyethylene film (PE-LD) on top of the metallized film using an adhesive via a bench lamination process. The laminated PE-LD film in this case replaces the EAA-film. In this approach, the laminate structure is similar to the final product in the end-use. The metal adhesion strength is found to be in good agreement with the strength measured for similar structures produced at pilot scale.
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