Diels-Alder Network Blends as Self-Healing Encapsulants for Liquid Metal-Based Stretchable Electronics.

Two dynamic covalent networks based on the Diels-Alder reaction were blended to exploit the properties of the dissimilar polymer backbones. Furan-functionalized polyether amines based on poly(propylene oxide) (PPO) FD4000 and polydimethylsiloxane (PDMS) FS5000 were mixed in a common solvent and reversibly cross-linked with the same bismaleimide DPBM. The morphology of the phase-separated blends is primarily controlled by the concentration of backbones. Increasing the PDMS content of the blends results in a dilute droplet morphology at 25 wt %, with a growing size and concentration of droplets and the formation of two separate PPO- and PDMS-rich layers at 50 wt %. Further increasing the PDMS content to 75 wt % leads to larger droplets and a thicker layer of the secondary phase. The hydrophobic PDMS phase creates a barrier against water, while the more hydrophilic PPO phase enhances the resistance against oxygen diffusion. Lowering the maleimide-to-furan stoichiometric ratio resulted in a decrease in cross-link density and thus more flexible and stretchable encapsulants. Changes in the stoichiometric ratio also affected the phase morphology due to resulting changes in phase separation and network formation kinetics. Lowering the stoichiometric ratio also resulted in enhanced self-healing properties of 96% at room temperature as a consequence of the increased chain mobility in the blended networks. The self-healing blends were used to encapsulate liquid metal circuits to create stretchable strain sensors with a linear electro-mechanical response without much drift or hysteresis, which could be efficiently recovered by 90% after the damage-healing cycles.

Fabrication of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Fibers Using Centrifugal Fiber Spinning: Structure, Properties and Application Potential.

Biobased and biodegradable polyhydroxyalkanoates (PHAs) are currently gaining momentum. Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) polymer has a useful processing window for extrusion and injection molding of packaging, agricultural and fishery applications with required flexibility. Processing PHBHHx into fibers using electrospinning or centrifugal fiber spinning (CFS) can further broaden the application area, although CFS remains rather unexplored. In this study, PHBHHx fibers are centrifugally spun from 4-12 wt.% polymer/chloroform solutions. Beads and beads-on-a-string (BOAS) fibrous structures with an average diameter (ϕav) between 0.5 and 1.6 µm form at 4-8 wt.% polymer concentrations, while more continuous fibers (ϕav = 3.6-4.6 µm) with few beads form at 10-12 wt.% polymer concentrations. This change is correlated with increased solution viscosity and enhanced mechanical properties of the fiber mats (strength, stiffness and elongation values range between 1.2-9.4 MPa, 11-93 MPa, and 102-188%, respectively), though the crystallinity degree of the fibers remains constant (33.0-34.3%). In addition, PHBHHx fibers are shown to anneal at 160 °C in a hot press into 10-20 µm compact top-layers on PHBHHx film substrates. We conclude that CFS is a promising novel processing technique for the production of PHBHHx fibers with tunable morphology and properties. Subsequent thermal post-processing as a barrier or active substrate top-layer offers new application potential.

Characterizing Mechanical, Heat Seal, and Gas Barrier Performance of Biodegradable Films to Determine Food Packaging Applications.

In an organic circular economy, biodegradable materials can be used as food packaging, and at end-of-life their carbon atoms can be recovered for soil enrichment after composting, so that new food or materials can be produced. Packaging functionality, such as mechanical, gas barrier, and heat-seal performance, of emerging biodegradable packaging, with a laminated, coated, monomaterial, and/or blended structure, is not yet well known in the food industry. This lack of knowledge, in addition to end-of-life concerns, high cost, and production limits is one of the main bottlenecks for broad implementation in the food industry. This study determines application areas of 10 films with a pragmatic approach based on an experimental broad characterization of packaging functionality. As a conclusion, the potential application of these materials is discussed with respect to industrial settings and food and consumer requirements, to support the implementation of commercially available, biodegradable, and, more specifically, compostable, materials for the identified food applications.

Extrusion and Injection Molding of Poly(3-Hydroxybutyrate-co-3-Hydroxyhexanoate) (PHBHHx): Influence of Processing Conditions on Mechanical Properties and Microstructure.

Biobased and biodegradable polyhydroxyalkanoates (PHAs) have great potential as sustainable packaging materials. However, improvements in their processing and mechanical properties are necessary. In this work, the influence of melt processing conditions on the mechanical properties and microstructure of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) is examined using a full factorial design of experiments (DoE) approach. We have found that strict control over processing temperature, mold temperature, screw speed, and cooling time leads to highly increased elongation at break values, mainly under influence of higher mold temperatures at 80 °C. Increased elongation of the moldings is attributed to relaxation and decreased orientation of the polymer chains together with a homogeneous microstructure at slower cooling rates. Based on the statistically substantiated models to determine the optimal processing conditions and their effects on microstructure variation and mechanical properties of PHBHHx samples, we conclude that optimizing the processing of this biopolymer can improve the applicability of the material and extend its scope in the realm of flexible packaging applications.

Screen Printed Antennas on Fiber-Based Substrates for Sustainable HF RFID Assisted E-Fulfilment Smart Packaging.

Intelligent packaging is an emerging technology, aiming to improve the standard communication function of packaging. Radio frequency identification (RFID) assisted smart packaging is of high interest, but the uptake is limited as the market needs cost-efficient and sustainable applications. The integration of screen printed antennas and RFID chips as smart labels in reusable cardboard packaging could offer a solution. Although paper is an interesting and recyclable material, printing on this substrate is challenging as the ink conductivity is highly influenced by the paper properties. In this study, the best paper/functional silver ink combinations were first selected out of 76 paper substrates based on the paper surface roughness, air permeance, sheet resistance and SEM characterization. Next, a flexible high frequency RFID chip (13.56 MHz) was connected on top of screen printed antennas with a conductive adhesive. Functional RFID labels were integrated in cardboard packaging and its potential application as reusable smart box for third party logistics was tested. In parallel, a web-based software application mimicking its functional abilities in the logistic cycle was developed. This multidisciplinary approach to developing an easy-scalable screen printed antenna and RFID-assisted smart packaging application is a good example for future implementation of hybrid electronics in sustainable smart packaging.

Oxygen Gas and UV Barrier Properties of Nano-ZnO-Coated PET and PHBHHx Materials Fabricated by Ultrasonic Spray-Coating Technique.

Ultrasonic spray-coating (USSC)-a wet chemical deposition method to deposit ultrathin (down to 20 nm) coatings-is being applied as a promising alternative deposition method for functional coatings due to an economical, simple, and precise coating process with easy control over its operating parameters. In this research, zinc oxide nanoparticles (ZnO NPs) were ultrasonically spray-coated on commercial-grade polyethylene terephthalate (PET) and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) films. The most suitable parameters for the ink composition, the ultrasonic spray-coating process, and the number of coating passes (up to 50×) were selected on the basis of a series of experiments. The oxygen gas barrier properties in terms of the oxygen transmission rate (OTR) of neat PET, and 3×, 5×, 10×, and 50× ZnO NP-coated PET and PHBHHx substrates were investigated. The OTR values for neat PET, and 3×, 5×, and 10× ZnO NP-coated PET substrates were found to be the same; however, a 5% reduction in OTR for 50× ZnO NP-coated PET substrate was observed compared to the neat PET substrate. No reduction in OTR was found for any above number of coating passes on PHBHHx substrates against the neat PHBHHx substrate. However, the ultraviolet (UV) tests of 3×, 5×, and 10× ZnO NP-coated PET and PHBHH× substrates revealed a significant decrease in percentage transmission for 10× coated PET and PHBHHx substrates as compared to their 3× and 5× ZnO NP-coated substrates, respectively. It was revealed from the study that the 50× ZnO NP coating of the PET substrate created a slight difference in OTR as compared to the reference substrate. However, the ultrasonic spray-coating method created a significant UV barrier effect for 3×, 5×, and 10× ZnO NP-coated PET and PHBHHx substrates, which demonstrates that the optimized coating method cannot be used to create a high oxygen barrier but can certainly be applied for UV barrier applications in food packaging. It is concluded that ultrasonic spray deposition of ZnO NPs on PET and PHBHHx materials has shown promising results for UV barrier properties, demonstrating the advantages of using this method compared to other coating methods with regard to cost-effectiveness, precise coating, and better process control.

Influence of Polymer Concentration and Nozzle Material on Centrifugal Fiber Spinning.

Centrifugal fiber spinning has recently emerged as a highly promising alternative technique for the production of nonwoven, ultrafine fiber mats. Due to its high production rate, it could provide a more technologically relevant fiber spinning technique than electrospinning. In this contribution, we examine the influence of polymer concentration and nozzle material on the centrifugal spinning process and the fiber morphology. We find that increasing the polymer concentration transforms the process from a beaded-fiber regime to a continuous-fiber regime. Furthermore, we find that not only fiber diameter is strongly concentration-dependent, but also the nozzle material plays a significant role, especially in the continuous-fiber regime. This was evaluated by the use of a polytetrafluoroethylene (PTFE) and an aluminum nozzle. We discuss the influence of polymer concentration on fiber morphology and show that the choice of nozzle material has a significant influence on the fiber diameter.

(Bio)polymer/ZnO Nanocomposites for Packaging Applications: A Review of Gas Barrier and Mechanical Properties.

Nanotechnology is playing a pivotal role in improving quality of life due to its versatile applications in many areas of research. In this regard, nanoparticles have gained significant importance. Zinc oxide nanoparticles (ZnO NPs) amongst other nanoparticles are being used in producing nanocomposites. Methods like solvent casting, solution casting, solvent volatilization, twin-screw extrusion, melt compounding and extrusion blow molding have been applied to produce ZnO NPs based (bio)polymer composites. These composites are of great interest in the research area of food packaging materials due to their improved multifunctional characteristics like their mechanical, barrier and antimicrobial properties. This paper gives an overview of the main methods to synthesize ZnO NPs, methods to incorporate ZnO NPs in (bio)polymers, and finally, the gas barrier and mechanical properties of the nanocomposites. As a conclusion, a maximum decline in oxygen, carbon dioxide and water vapor permeability was reported as 66%, 17% and 38% respectively, while tensile strength and young's modulus were observed to increase by 32% and 57% respectively, for different (bio)polymer/ZnO nanocomposites.

Hydrothermal synthesis of ZnO nanorods: a statistical determination of the significant parameters in view of reducing the diameter.

In this paper a 2(8-4) fractional factorial design of experiments is applied to identify the important parameters that affect the average diameter of ZnO rods, synthesized by means of a hydrothermal procedure. A water-based Zn(2+) precursor is used for the formation of one-dimensional ZnO particles, without the presence of an organic additive. Results indicate that, at the investigated levels, four of the parameters have a significant effect on the mean diameter. These are the temperature, the heating rate, stirring and an ultrasonic pre-treatment of the precursor solution. Experiments carried out with zinc acetate and zinc chloride do not show a significant difference in rod diameter. Other parameters that do not show a significant effect are the concentration of Zn(2+), the molar ratio between the hydroxyl and the zinc ions, and the reaction time. Interactions are observed between stirring and an ultrasonic pre-treatment and between the zinc concentration and the OH:Zn ratio. By fixing the significant factors at their optimal value it is possible to decrease the mean diameter. The particles are characterized by means of x-ray diffraction (XRD) and transmission electron microscopy (TEM).