Green composites based on thermoplastic starch reinforced with micro- and nano-cellulose by melt blending - A review.

Starch is a biodegradable biopolymer, a sustainable material that can replace conventional petrochemical-based plastics. However, starch has some limitations, as it must be processed by heating and treated mechanically with a plasticizer to become thermoplastic starch (TPS). Different variables such as mixing speeds, amount, and kind of plasticizers play a vital role in preparing TPS by melting. Despite this, the properties of the TPS are not comparable with those of traditional plastics. To overcome this limitation, microcellulose or nanocellulose is added to TPS by melt mixing, including the extrusion and internal mixing process, which enables large-scale production. This review aims to compile several studies that evaluate the effect of plasticizers, as well as the relevance of incorporating different cellulosic fillers of different dimensions on the properties of TPS obtained by melt mixing. Potential applications of these materials in food packaging, biomedical applications, and other opportunities are also described.

Cytocompatible drug delivery hydrogels based on carboxymethylagarose/chitosan pH-responsive polyelectrolyte complexes.

Several drugs are chemically unstable in the gastric environment and have low bioavailability restricted by intestinal absorption, which motivates the development of alternative routes for drug release, such as transdermal drug carriers for drug delivery to specific areas of the skin. Herein, novel polyelectrolyte complexes (PEC) consisting of carboxymethylagarose (CMA) and chitosan (CS) were prepared. pH-responsive CMA/CS hydrogels were obtained by mixing CMA and CS at various weight ratios. Swelling ratio was modulated by varying the CMA and CS weight ratio, and the highest swelling values were achieved for 2:1 wt% hydrogels at 25 °C and pH 6.0. PEC films were characterized by ATR-FTIR spectroscopy, TGA, DSC, and SEM. Results indicated that CMA and CS were successfully crosslinked by ionic complexation. As a model drug, diclofenac sodium (DS) was loaded in CMA/CS PECs. Association efficiency and loading capacity were ca. 69% and 79%, respectively, exhibiting 67% cumulative release after 72 h at 37 °C and pH 6.0 through Fickian diffusion mechanism. Viability assay of immortalized human keratinocyte (HaCat) cells showed ca. 100% survival in the presence of hydrogels and DS. Therefore, this work suggests that CMA/CS PECs can be applied as pH-responsive carriers for dermal drug delivery.

Study of the effect of the addition of plasticizers on the physical properties of biodegradable films based on kefiran for potential application as food packaging.

Spectroscopies analysis indicated that kefiran contains branched hexasaccharide repeating units. Neat kefiran films, 2 and 5% w/w of glycerol, d-glucitol, d-galactitol, d-mannitol, and d-limonene were incorporated as plasticizers. Neat and plasticized kefiran films were characterized by physical, thermal, mechanical, optical, and water solubilization properties. Neat kefiran had a glass transition temperature (Tg) of -20 ± 2 °C and, with the addition of plasticizers between -15 to -17 ± 2 °C. The values were close to the neat kefiran, and the results could be attributed to a lower amount of plasticizer used. The solubility of the glycerol plasticized films increases by 33% and decreased with the concentration of other plasticizers in comparison with the neat kefiran. d-glucitol and d-galactitol decreased the microhardness and Young's Modulus of films around 30% and 74% respectively, obtaining more flexible kefiran films. Kefiran based films could find applications as potential materials in the food-packaging industry.

Mechanical and Antimicrobial Polyethylene Composites with CaO Nanoparticles.

Low-density polyethylene composites containing different sizes of calcium oxide (CaO) nanoparticles were obtained by melt mixing. The CaO nanoparticles were synthesized by either the sol-gel or sonication methods, obtaining two different sizes: ca. 55 nm and 25 nm. These nanoparticles were used either as-synthesized or were modified organically on the surface with oleic acid (Mod-CaO), at concentrations of 3, 5, and 10 wt% in the polymer. The Mod-CaO nanoparticles of 25 nm can act as nucleating agents, increasing the polymer's crystallinity. The Young's Modulus increased with the Mod-CaO nanoparticles, rendering higher reinforcement effects with an increase as high as 36%. The reduction in Escherichia coli bacteria in the nanocomposites increased with the amount of CaO nanoparticles, the size reduction, and the surface modification. The highest antimicrobial behavior was found in the composites with a Mod-CaO of 25 nm, presenting a reduction of 99.99%. This strong antimicrobial effect can be associated with the release of the Ca2+ from the composites, as studied for the composite with 10 wt% nanoparticles. The ion release was dependent on the size of the nanoparticles and their surface modification. These findings show that CaO nanoparticles are an excellent alternative as an antimicrobial filler in polymer nanocomposites to be applied for food packaging or medical devices.

Effect of bioglass nanoparticles on the properties and bioactivity of poly(lactic acid) films.

Bioglass nanoparticles (n-BGs, 54SiO2 :40CaO:6P2 O5 mol %) with about 27 nm diameter were synthesized by the sol-gel method and incorporated into a poly(lactic acid) (PLA) matrix by the melting process in order to obtain nanocomposites with filler contents of 5, 10, and 25 wt %. Our results showed that during the cooling scan, the crystallization temperature (Tc ) of the PLA/n-BG nanocomposites decreased 13°C as compared to neat PLA. The presence of nanoparticles also decreased the thermal stability of the PLA matrix, as nanocomposites presented up to about 20°C lower degradation temperatures in a nitrogen atmosphere. The presence of n-BG increased the stiffness of the polymer matrix, and for instance the composite with 25 wt % of filler presented about 52.6% higher Young's modulus than neat PLA. n-BG incorporation into PLA increased also the hydrolytic degradation of the polymer over time. When the PLA composites were immersed in simulated body fluid, an apatite layer was formed on their surface, as verified by Fourier transform infrared, X-Ray Diffraction (XRD), and scanning electron microscopy-EDS, showing that the presence of n-BG induced bioactivity on the PLA matrix. Moreover, the viability of cervical uterine adenocarcinoma cells was higher on PLA/n-BG nanocomposite with 25 wt % of filler. The presence of n-BG barely gave an antibacterial effect on the polymer matrix, despite the well-known biocidal properties of these nanoparticles. Our results show that the presence of n-BGs is a proper route for improving the bioactivity of PLA with potential application in tissue engineering.

Effect of CaCO3 Nanoparticles on the Mechanical and Photo-Degradation Properties of LDPE.

CaCO3 nanoparticles of around 60 nm were obtained by a co-precipitation method and used as filler to prepare low-density polyethylene (LDPE) composites by melt blending. The nanoparticles were also organically modified with oleic acid (O-CaCO3) in order to improve their interaction with the LDPE matrix. By adding 3 and 5 wt% of nanofillers, the mechanical properties under tensile conditions of the polymer matrix improved around 29%. The pure LDPE sample and the nanocomposites with 5 wt% CaCO3 were photoaged by ultraviolet (UV) irradiation during 35 days and the carbonyl index (CI), degree of crystallinity (χc), and Young's modulus were measured at different times. After photoaging, the LDPE/CaCO3 nanocomposites increased the percent crystallinity (χc), the CI, and Young's modulus as compared to the pure polymer. Moreover, the viscosity of the photoaged nanocomposite was lower than that of photoaged pure LDPE, while scanning electron microscopy (SEM) analysis showed that after photoaging the nanocomposites presented cavities around the nanoparticles. These difference showed that the presence of CaCO3 nanoparticles accelerate the photo-degradation of the polymer matrix. Our results show that the addition of CaCO3 nanoparticles into an LDPE polymer matrix allows future developments of more sustainable polyethylene materials that could be applied as films in agriculture. These LDPE-CaCO3 nanocomposites open the opportunity to improve the low degradation of the LDPE without sacrificing the polymer's behavior, allowing future development of novel eco-friendly polymers.

Preparation and characterization of maleoylagarose/PNIPAAm graft copolymers and formation of polyelectrolyte complexes with chitosan.

A water soluble derivative in 98% yield with 23.1% incorporation of maleoyl groups was obtained by esterification of agarose with maleic anhydride. Graft copolymers were synthesized through vinyl groups of maleoylagarose with N-isopropylacrylamide using ceric ammonium nitrate or ammonium persulfate as initiator, by conventional method or microwave irradiation. High nitrogen content (4.6%) was obtained in the grafting process using ceric ammonium nitrate as initiator without microwave irradiation. Copolymers were characterized by FT-IR and NMR spectroscopies, TGA, DSC and morphological analysis by AFM and SEM microscopy, confirming the grafting of PNIPAAm onto polysaccharide backbone. Hydrogel films were obtained by ionic complexation between opposite charged groups of maleoylagarose-g-poly(N-isopropylacrylamide) and chitosan. The swelling of 1:1w/v maleoylagarose-g-PNIPAAm:chitosan film was higher than 2:1w/v film at 25 and 37°C. 53% release in vitro of diclofenac sodium from 1:1w/v maleoylagarose-g-PNIPAAm:chitosan was obtained at 37°C and pH 6.0 with <0.5 diffusional constant values.