In this work, a new eco-friendly method for the treatment of poly(3-hydroxybutyrate) (PHB) as a candidate for food packaging applications is proposed. Poly(3-hydroxybutyrate) was modified by bacterial cellulose nanofibers (BC) using a melt compounding technique and by plasma treatment or zinc oxide (ZnO) nanoparticle plasma coating for better properties and antibacterial activity. Plasma treatment preserved the thermal stability, crystallinity and melting behavior of PHB‒BC nanocomposites, regardless of the amount of BC nanofibers. However, a remarkable increase of stiffness and strength and an increase of the antibacterial activity were noted. After the plasma treatment, the storage modulus of PHB having 2 wt % BC increases by 19% at room temperature and by 43% at 100 °C. The tensile strength increases as well by 21%. In addition, plasma treatment also inhibits the growth of Staphylococcus aureus and Escherichia coli by 44% and 63%, respectively. The ZnO plasma coating led to important changes in the thermal and mechanical behavior of PHB‒BC nanocomposite as well as in the surface structure and morphology. Strong chemical bonding of the metal nanoparticles on PHB surface following ZnO plasma coating was highlighted by infrared spectroscopy. Moreover, the presence of a continuous layer of self-aggregated ZnO nanoparticles was demonstrated by scanning electron microscopy, ZnO plasma treatment completely inhibiting growth of Staphylococcus aureus. A plasma-treated PHB‒BC nanocomposite is proposed as a green solution for the food packaging industry.
Submerged liquid plasma (SLP) is a new and promising method to modify powder materials. Up to now, this technique has been mostly applied to carbonaceous materials, however, SLP shows great potential as a low-cost and environmental-friendly method to modify cellulose. In this work we demonstrate the modification of microcrystalline cellulose (MCC) by applying the SLP combined with ultrasonication treatments. The plasma generated either in an inert (argon) or reactive (argon: oxygen or argon:nitrogen) gas was used in MCC dispersions in water or acetonitrile:water mixtures. An enhanced defibrillation of MCC has been observed following the application of SLP. Furthermore, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy have been applied to investigate the surface functionalization of MCC with oxygen or nitrogen moieties. Depending on the plasma treatment applied, poly (3-hydroxybutyrate) composites fabricated with the plasma modified cellulose fibers showed better thermal stability and mechanical properties than pristine PHB. This submerged liquid plasma processing method offers a unique approach for the activation of cellulose for defibrillation and functionalization, aiming towards an improved reinforcing ability of biopolymers.
Carbon nanowalls (CNWs) functionalization allows the tailoring of some of their properties after they have been synthesized. Herewith we report on post‐synthesis CNWs functionalization by plasma treatments. Radiofrequency plasmas generated in hydrogen, oxygen, nitrogen, tetrafluoroethane, and sulfur hexafluoride admixed to argon, were used. The changes of morphology, structure, chemical composition were determined by SEM, FTIR, Raman Spectroscopy, specifically for each gas mixture. The results point out to the surface erosion, the functional groups attachment, or to thin film coverage of CNWs material. Such processes strongly influence the material properties, as exemplified by the wettability: superhydrophilic or superhydrophobic surfaces are obtained starting from the same base CNWs material.
Using plasma in conjunction with fluorinated compounds is widely encountered in material processing. We discuss several plasma techniques for surface fluorination: deposition of fluorocarbon thin films either by magnetron sputtering of polytetrafluoroethylene targets, or by plasma-assisted chemical vapor deposition using tetrafluoroethane as a precursor, and modification of carbon nanowalls by plasma treatment in a sulphur hexafluoride environment. We showed that conformal fluorinated thin films can be obtained and, according to the initial surface properties, superhydrophobic surfaces can be achieved.
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