Biobased sustainable materials made from starch and plasma/ultrasound modified Agave fibers: Structural and water barrier performance.

This study aims to investigate the effect of green modification methods (ultrasound and plasma treatment) on a by-product of the tequila industry (Agave fibers), which can be useful as raw material to elaborate biodegradable and hydrophobic starch films. FTIR analysis indicated a decrease of hydrophilic lignocellulosic components, since the cavitation and etching effect of ultrasound/plasma treatment reduced the large number of hydroxyl groups of the fibers. The inclusion of ultrasound/plasma modified fibers in the starch matrix limited the starch-glycerol interactions, reducing the free volume of the starch and the binding sites for water. Therefore, the solubility (%S), swelling (%W) and water vapor permeance (WVPe) of the films decreased from 27 to 16%, 57 to 50% and 0.37 to 0.21 g/day m2Pa, respectively. Furthermore, the water contact angle (WCA) and relative crystallinity values increased. The results indicated that the treatments are suitable green technologies to obtain hydrophobic fillers useful to develop sustainable materials.

Covalent Functionalization of Graphene Oxide with Fructose, Starch, and Micro-Cellulose by Sonochemistry.

In this work, we report the synthesis of graphene oxide (GO) nanohybrids with starch, fructose, and micro-cellulose molecules by sonication in an aqueous medium at 90 °C and a short reaction time (30 min). The final product was washed with solvents to extract the nanohybrids and separate them from the organic molecules not grafted onto the GO surface. Nanohybrids were chemically characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy and analyzed by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and X-ray diffraction (XRD). These results indicate that the ultrasound energy promoted a chemical reaction between GO and the organic molecules in a short time (30 min). The chemical characterization of these nanohybrids confirms their covalent bond, obtaining a grafting percentage above 40% the weight in these nanohybrids. This hybridization creates nanometric and millimetric nanohybrid particles. In addition, the grafted organic molecules can be crystallized on GO films. Interference in the ultrasound waves of starch hybrids is due to the increase in viscosity, leading to a partial hybridization of GO with starch.

Transparent Low Electrostatic Charge Films Based on Carbon Nanotubes and Polypropylene. Homopolymer Cast Films.

Use of multi-wall carbon nanotubes (MWCNTs) in external layers (A-layers) of ABA-trilayer polypropylene films was investigated, with the purpose of determining intrinsic and extrinsic factors that could lead to antistatic behavior of transparent films. The incorporation of 0.01, 0.1, and 1 wt % of MWCTNs in the A-layers was done by dilution through the masterbatch method. Masterbatches were fabricated using isotactic polypropylene (iPP) with different melt flow indexes 2.5, 34, and 1200 g/10 min, and using different ultrasound assist methods. It was found that films containing MWCNTs show surface electrical resistivity of 1012 and 1016 Ω/sq, regardless of the iPP melt flow index (MFI) and masterbatch fabrication method. However, electrostatic charge was found to depend upon the iPP MFI, the ultrasound assist method and MWCNT concentration. A percolation electron transport mechanism was determined most likely responsible for this behavior. Optical properties for films containing MWCNTs do not show significant differences compared to the reference film at MWCNT concentrations below 0.1 wt %. However, an enhancement in brightness was observed, and it was attributed to ordered iPP molecules wrapping the MWCNTs. Bright transparent films with low electrostatic charge were obtained even for MWCNTs concentrations as low as 0.01 wt %.

Early Stages of Antibacterial Damage of Metallic Nanoparticles by TEM and STEM-HAADF.

BACKGROUND: Propagation of pathogens has considered an important health care problem due to their resistance against conventional antibiotics. The recent challenge involves the design of functional alternatives such as nanomaterials, used as antibacterial agents. Early stages of antibacterial damage caused by metallic nanoparticles (NPs) were studied by Transmission Electron Microscopy (TEM) and combined Scanning Transmission Electron Microscopy with High Angle Annular Dark Field (STEM-HAADF), aiming to contribute to the elucidation of the primary antibacterial mechanism of metallic NPs. METHODS: We analyze the NPs morphology by TEM and their antibacterial activity (AA) with different amounts of Ag and Cu NPs. Cultured P. aeruginosa were interacted with both NPs and processed by TEM imaging to determine NPs adhesion into bacteria wall. Samples were analyzed by combined STEM-HAADF to determine the NPs penetration into bacterium and elemental mapping were done. RESULTS: Both NPs displays AA depending on NPs concentration. TEM images show NPs adhesion on bacterial cells, which produces morphological changes in the structure of the bacteria. STEM-HAADF also proves the NPs adhesion and penetration by intracellular localization, detecting Ag/Cu species analyzed by elemental mapping. Moreover, the relative amount of phosphorus (P) and sulfur (S) increases slightly in P. aeruginosa with the presence of NPs. These elements are associated with damaged proteins of the outer cell membrane. CONCLUSIONS: Combined microscopy analyses suggest that the early stages of antibacterial damage caused by alteration of bacterial cell wall, and can be considered a powerful tool aiming to understand the primary antibacterial mechanism of NPs.

Metamaterial Behavior of Polymer Nanocomposites Based on Polypropylene/Multi-Walled Carbon Nanotubes Fabricated by Means of Ultrasound-Assisted Extrusion.

Metamaterial behavior of polymer nanocomposites (NCs) based on isotactic polypropylene (iPP) and multi-walled carbon nanotubes (MWCNTs) was investigated based on the observation of a negative dielectric constant (ε'). It is demonstrated that as the dielectric constant switches from negative to positive, the plasma frequency (ωp) depends strongly on the ultrasound-assisted fabrication method, as well as on the melt flow index of the iPP. NCs were fabricated using ultrasound-assisted extrusion methods with 10 wt % loadings of MWCNTs in iPPs with different melt flow indices (MFI). AC electrical conductivity (σ(AC)) as a function of frequency was determined to complement the electrical classification of the NCs, which were previously designated as insulating (I), static-dissipative (SD), and conductive (C) materials. It was found that the SD and C materials can also be classified as metamaterials (M). This type of behavior emerges from the negative dielectric constant observed at low frequencies although, at certain frequencies, the dielectric constant becomes positive. Our method of fabrication allows for the preparation of metamaterials with tunable ωp. iPP pure samples show only positive dielectric constants. Electrical conductivity increases in all cases with the addition of MWCNTs with the largest increases observed for samples with the highest MFI. A relationship between MFI and the fabrication method, with respect to electrical properties, is reported.

Ultrasound-Assist Extrusion Methods for the Fabrication of Polymer Nanocomposites Based on Polypropylene/Multi-Wall Carbon Nanotubes.

Isotactic polypropylenes (iPP) with different melt flow indexes (MFI) were used to fabricate nanocomposites (NCs) with 10 wt % loadings of multi-wall carbon nanotubes (MWCNTs) using ultrasound-assisted extrusion methods to determine their effect on the morphology, melt flow, and electrical properties of the NCs. Three different types of iPPs were used with MFIs of 2.5, 34 and 1200 g/10 min. Four different NC fabrication methods based on melt extrusion were used. In the first method melt extrusion fabrication without ultrasound assistance was used. In the second and third methods, an ultrasound probe attached to a hot chamber located at the exit of the die was used to subject the sample to fixed frequency and variable frequency, respectively. The fourth method is similar to the first method, with the difference being that the carbon nanotubes were treated in a fluidized air-bed with an ultrasound probe before being used in the fabrication of the NCs with no ultrasound assistance during extrusion. The samples were characterized by MFI, Optical microscopy (OM), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), electrical surface resistivity, and electric charge. MFI decreases in all cases with addition of MWCNTs with the largest decrease observed for samples with the highest MFI. The surface resistivity, which ranged from 1013 to 105 Ω/sq, and electric charge, were observed to depend on the ultrasound-assisted fabrication method as well as on the melt flow index of the iPP. A relationship between agglomerate size and area ratio with electric charge was found. Several trends in the overall data were identified and are discussed in terms of MFI and the different fabrication methods.