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ABSTRACT:Grafting of polyethylenes is an important method used in the modification of polyolefins with functional groups. Lately, the use of extruders as polymerization reactors has increased considerably. However, knowledge of the details of the reaction in the extruder is still limited. In this investigation, the grafting of various commercial polyethylenes, high-density polyethylenes (HDPEs), and linear low-density polyethylenes (LLDPEs) with diethyl maleate (DEM) was carried out in two corotating twinscrew extruders with different screw configurations and extrusion conditions. Two initiators at different concentrations were used. It was found that when the initiator level was raised in the LLDPEs the grafting degree increased and the molecular weight distribution of the grafted LLDPE2 did not show appreciable differences when they were compared to the virgin resin. On the other hand, the terminal vinyl group concentrations decreased at the expense of increasing the trans unsaturation concentrations. This last result is consistent with the formation of long-chain branching. Additionally, the weight-average molecular weight of grafted high-density polyethylene (HDPE1-g-DEM) decreased. The grafting efficiencies were consistent with the attained residence times and also with the kinetics of the decomposition of the peroxides.

The development of bio-based materials has been a consequence of the environmental awareness generated over time. The versatility of native starch is a promising starting point for manufacturing environmentally friendly materials. This work aims to compile information on the advancements in research on thermoplastic starch (TPS) nanocomposites after the addition of mainly these four nanofillers: natural montmorillonite (MMT), organically modified montmorillonite (O-MMT), cellulose nanocrystals (CNC), and cellulose nanofibers (CNF). The analyzed properties of nanocomposites were mechanical, barrier, optical, and degradability. The most important results were that as the nanofiller increases, the TPS modulus and strength increase; however, the elongation decreases. Furthermore, the barrier properties indicate that that the incorporation of nanofillers confers superior hydrophobicity. However, the optical properties (transparency and luminosity) are mostly reduced, and the color variation is more evident with the addition of these fillers. The biodegradability rate increases with these nanocompounds, as demonstrated by the study of the method of burial in the soil. The results of this compilation show that the compatibility, proper dispersion, and distribution of nanofiller through the TPS matrix are critical factors in overcoming the limitations of starch when extending the applications of these biomaterials. TPS nanocomposites are materials with great potential for improvement. Exploring new sources of starch and natural nano-reinforcement could lead to a genuinely eco-friendly material that can replace traditional polymers in applications such as packaging.

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A hydrogen peroxide (H2O2) sensor and biosensor based on modified multi-walled carbon nanotubes (CNTs) with titanium dioxide (TiO2) nanostructures was designed and evaluated. The construction of the sensor was performed using a glassy carbon (GC) modified electrode with a TiO2–CNT film and Prussian blue (PB) as an electrocalatyzer. The same sensor was also employed as the basis for H2O2 biosensor construction through further modification with horseradish peroxidase (HRP) immobilized at the TiO2–fCNT film. Functionalized CNTs (fCNTs) and modified TiO2–fCNTs were characterized by Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), and X-Ray DifFraction (XRD), confirming the presence of anatase over the fCNTs. Depending on the surface charge, a solvent which optimizes the CNT dispersion was selected: dimethyl formamide (DMF) for fCNTs and sodium dodecylsulfate (SDS) for TiO2–fCNTs. Calculated values for the electron transfer rate constant (ks) were 0.027 s−1 at the PB–fCNT/GC modified electrode and 4.7 × 10−4 s−1 at the PB–TiO2/fCNT/GC electrode, suggesting that, at the PB–TiO2/fCNT/GC modified electrode, the electronic transfer was improved. According to these results, the PB–fCNT/GC electrode exhibited better Detection Limit (LD) and Quantification Limit (LQ) than the PB–TiO2/fCNT/GC electrode for H2O2. However, the PB film was very unstable at the potentials used. Therefore, the PB–TiO2/fCNT/GC modified electrode was considered the best for H2O2 detection in terms of operability. Cyclic Voltammetry (CV) behaviors of the HRP–TiO2/fCNT/GC modified electrodes before and after the chronoamperometric test for H2O2, suggest the high stability of the enzymatic electrode. In comparison with other HRP/fCNT-based electrochemical biosensors previously described in the literature, the HRP–fCNTs/GC modified electrode did not show an electroanalytical response toward H2O2.

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