High performance poly(lactic acid)/poly(ether-block-amide) blend-based bionanocomposites containing carbon nanotubes and/or organoclay.

High-performance poly(lactic acid) (PLA) blend-based composites were fabricated with a poly(ether-block-amide) (PEBA) elastomer acting as the blend counterpart. It was confirmed that a compatibilizer (ADR) enhanced the interaction between PLA and PEBA. Carbon nanotubes (CNTs) and organoclay (30B) were added individually and simultaneously into the blend to produce bionanocomposites. Morphological results showed that CNTs were mainly dispersed in PEBA domains, whereas 30B was mainly localized at the interfacial region of PLA and PEBA phases. The selective localization of added CNTs and 30B led to significant modification of the properties of the compatibilized PLA/PEBA blend. The brittleness and flammability of PLA were evidently improved after forming the bionanocomposites. Differential scanning calorimetry results revealed that CNTs and 30B assisted the crystallization of both PLA and PEBA in the composites, with CNTs providing superior nucleation efficiency to 30B. Thermogravimetric analysis revealed the thermal stability enhancement of the blend after adding CNTs and/or 30B, with up to 16 °C increase at 20 wt% loss with inclusion of 2 phr 30B. Addition of CNTs and/or 30B improved the blend's anti-dripping performance during burning tests, and CNT exhibited better anti-dripping efficiency. Ductility of PLA was drastically improved after forming the compatibilized blend, and further improved with incorporation of CNTs and/or 30B (increased from 9 % for neat PLA to 252 % for the hybrid composite containing CNT/30B). The impact strength of 1 phr CNTs-added composite was about 3 times that of PLA. Rheological properties indicated the (pseudo)network formation of added filler(s), leading to a significant reduction in electrical resistivity, up to six orders of magnitude with addition of 3 phr CNTs.

Fabrication and Characterization of PLA/PBAT Blends, Blend-Based Nanocomposites, and Their Supercritical Carbon Dioxide-Induced Foams.

In this study, a twin-screw extruder was used to fabricate poly(lactic acid) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT) blends and blend-based nanocomposites with carbon nanotube (CNT) or nanocarbon black (CB) as nanofillers. The fabricated samples were subsequently treated with supercritical carbon dioxide (scCO2) to fabricate the corresponding foams. Bi-phasic morphology and selective distribution of CNTs or CBs in the PBAT phase were observed in the blends/composites through scanning electron microscopy. After the scCO2 treatment, the selective foaming of the PBAT phase in the prepared blends/composites was confirmed. The cellular structure of PBAT phase in scCO2-treated blends is similar to the size/shape of PBAT domains in untreated blends or treated neat PBAT foam. The addition of CNTs or CBs in the blends led to a slight reduction in cell size of the foamed PBAT phase, demonstrating CNT/CB-induced cell nucleation. Differential scanning calorimetry (DSC) results showed that CNTs and CBs played as nucleating agents and increased the initial crystallization temperature up to 14 °C compared with neat PBAT for PBAT in different composites during cooling. The scCO2 treatment induced the bimodal stability of PBAT crystals in different samples, which melted mainly in two temperature regions in DSC studies. Thermogravimetric analyses revealed that compared with parent blends, the addition of CNTs or CBs increased the temperature at 80 wt.% loss (degradation of PBAT portion) up to 6 °C. The electrical resistivity decreased by more than six orders of magnitude for certain CNT- or CB-added composites compared with the parent blends. The hardness of the blends slightly increased after forming the corresponding composites and then declined after the scCO2 treatment.

Physical properties of cellulose nanocrystal/magnesium oxide/chitosan transparent composite films for packaging applications.

Hitherto unreported hybrid nanofillers (CNC:MgO) reinforced chitosan (CTS) based composite (CNC:MgO)/CTS films were synthesized using a solution-casting blend technique and synergistic effect of hybrid nanofiller in terms of properties enhancement were investigated. Optical microscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) technique, fourier-transform infrared spectroscopy (FTIR), and field emission scanning electron microscopy (FESEM) were used to characterize the films. The hybrid nanofiller considerably changed the transparency and color of the CTS films. The tensile strengths of (3 wt%) CNC/CTS, (3 wt%) MgO/CTS, (1:1)(CNC:MgO)/CTS, (1:2)(CNC:MgO)/CTS and (2:1)(CNC:MgO)/CTS films were 27.49 %, 35.60 %, 91.62 %, 38.22 %, and 29.32 % higher than pristine CTS films respectively, while the water vapor permeation were 28.21 %, 30.77 %, 34.62 %, 38.46 %, and 37.44 % lower than pristine CTS film, respectively. Moreover, the CTS composite films exhibited an improvement in overall water barrier properties after incorporating hybrid nanofillers. Our observations suggest that chitosan-based hybrid nanofiller composite films are a good replacement for plastic-based packaging materials within the food industry.

Design and synthesis of polypyrrole conductive ink based on sulfated chitosan for bactericide carbendazim detection.

Conductive polymers (CPs) are typically insoluble in solvents, and devising biocompatible hydrophilic CPs is challenging and imperative to expand the applications of CPs. Herein, sulfated chitosan (SCS) is used as a green dopant instead of toxic poly(styrene sulfonate) (PSS), and SCS:polypyrrole (SCS:PPy) conductive ink is prepared by in situ polymerization. Due to the complex structure between PPy and SCS polyanion, the synthesized SCS:PPy dispersion forms a well-connected electric pathway and confers superior conductivity, dispersion stability, good film-forming ability, and high electrical stability. As proof of our concept, electrochemical sensing utilizing an SCS:PPy-modified screen-printed carbon electrode (SPCE) was performed towards carbendazim (CBZ). The SCS:PPy on the SPCE surface displayed greater sensitivity to CBZ because the conductive complex structure eased the electrocatalytic action of SCS:PPy by dramatically increasing the current intensity of CBZ oxidation and notably ameliorating stability. The sensor unveils the lowest detection value of 1.02 nM with a linear range of 0.05 to 906 µM for sensing trace CBZ by utilizing the pulse voltammetry technique. Interestingly, this senor shows excellent selectivity towards CBZ due to the formation of substantial interactions between SCS:PPy and CBZ, as demonstrated by molecular simulation studies. Furthermore, this sensor can precisely monitor CBZ in actual fruit and river water samples with satisfactory results. This study sheds light on the design and synthesis of sustainable hydrophilic CPs in the fabrication of sensors.

Protein-Aided Synthesis of Copper-Integrated Polyaniline Nanocomposite Encapsulated with Reduced Graphene Oxide for Highly Sensitive Electrochemical Detection of Dimetridazole in Real Samples.

Dimetridazole (DMZ) is a derivative of nitroimidazole and is a veterinary drug used as an antibiotic to treat bacterial or protozoal infections in poultry. The residues of DMZ cause harmful side effects in human beings. Thus, we have constructed a superior electrocatalyst for DMZ detection. A copper (Cu)-integrated poly(aniline) (PANI) electrocatalyst (PANI-Cu@BSA) was prepared by using a one-step method of biomimetic mineralization and polymerization using bovine serum albumin (BSA) as a stabilizer. Then, the synthesized PANI-Cu@BSA was encapsulated with reduced graphene oxide (rGO) using an ultrasonication method. The PANI-Cu@BSA/rGO nanocomposite had superior water dispersibility, high electrical conductivity, and nanoscale particles. Moreover, a PANI-Cu@BSA/rGO nanocomposite-modified, screen-printed carbon electrode was used for the sensitive electrochemical detection of DMZ. In phosphate buffer solution, the PANI-Cu@BSA/rGO/SPCE displayed a current intensity greater than PANI-Cu@BSA/SPCE, rGO/SPCE, and bare SPCE. This is because PANI-Cu@BSA combined with rGO increases fast electron transfer between the electrode and analyte, and this synergy results in analyte-electrode junctions with extraordinary conductivity and active surface areas. PANI-Cu@BSA/rGO/SPCE had a low detection limit, a high sensitivity, and a linear range of 1.78 nM, 5.96 µA µM-1 cm-2, and 0.79 to 2057 µM, respectively. The selective examination of DMZ was achieved with interfering molecules, and the PANI-Cu@BSA/rGO/SPCE showed excellent selectivity, stability, repeatability, and practicability.

Synthesis of High-Value Bio-Based Polyamide 12,36 Microcellular Foams with Excellent Dimensional Stability and Shape Recovery Properties.

The search for alternatives to petroleum-based thermoplastic polyamide elastomers (TPAEs) has recently drawn great interest. In this study, a bio-massed TPAE, PA12,36, was synthesized using 1,12-dodecanediamine (DDA) and fatty dimer acid (FDA, PripolTM1009) precursors via catalyst and solvent-free melt polycondensation. The molecular structure and molecular weight of the PA12,36 were characterized by 1H NMR, FTIR, and GPC. PA12,36 displayed a low melting temperature of 85.8 °C, an initial degradation temperature of 425 °C, and a glass-transition temperature of 30.4 °C, whereas it sustained satisfactory tensile strength (10.0 MPa) and superior strain at break (1378%). Furthermore, PA12,36 was foamed by supercritical CO2, and the cell size, cell density, and porosity were determined. The entangled long-chained FDA component generated a physically crosslinked network, which promoted the melt viscosity of PA12,36 against elongations of foam cell growth and increased foamability significantly. As a result, uniform structured cellular foams with a cell diameter of 15-24 µm and high cell density (1011 cells/cm3-1012 cells/cm3) were successfully achieved. The foaming window was widened from 76 to 81 °C, and the expansion ratio was increased from 4.8 to 9.6. Additionally, PA12,36 foam with a physically crosslinked structure presented a better creep shape recovery percentage (92-97.9%) and sturdier dimensional stability. This bio-based PA12,36 foam is a promising candidate to replace petroleum-based thermoplastic elastomer foams for engineering applications, particularly shoe soles.

Modifications of Phase Morphology, Physical Properties, and Burning Anti-Dripping Performance of Compatibilized Poly(butylene succinate)/High-Density Polyethylene Blend by Adding Nanofillers.

A twin-screw extruder was used to fabricate poly(butylene succinate) (PBS)/high-density polyethylene (HDPE) blends (7:3 weight ratio) and blend-based nanocomposites. Carbon nanotubes (CNTs), graphene nanoplatelets (GNPs), and organoclays (15A and 30B) served as the nanofiller, while maleated HDPE (PEgMA) acted as an efficient compatibilizer for the blend. In the composites, individual nanofillers were mostly localized in HDPE domains, but some fillers were also observed at PBS-HDPE interfaces. The sea-island morphology of the compatibilized blend evolved into a pseudo-co-continuous morphology in the composites. Differential scanning calorimetry results confirmed that PEgMA with HDPE evidently accelerated the crystallization of PBS in the blend. The possible nucleation effect of added fillers on PBS crystallization was obscured by the formation of quasi-connected HDPE domains, causing fewer PBS nucleation sites. The presence of nanofillers improved the thermal stability and burning anti-dripping behavior of the parent blend. The anti-dripping efficiency of added fillers followed the sequence CNT > 15A > 30B > GNP. The rigidity of the blend was increased after the formation of nanocomposites. In particular, adding GNP resulted in 19% and 31% increases in the Young's modulus and flexural modulus, respectively. The development of a pseudo-network structure in the composites was confirmed by measurement of rheological properties. The electrical resistivity of the blend was reduced by more than six orders of magnitude at 3 phr CNT loading, demonstrating the achievement of double percolation morphology.

Polycarbonate/Poly(vinylidene fluoride)-Blend-Based Nanocomposites-Effect of Adding Different Carbon Nanofillers/Organoclay.

Carbon black (CB), carbon nanotubes (CNTs), and graphene nanoplatelets (GnPs) individually or doubly served as reinforcing fillers in polycarbonate (PC)/poly(vinylidene fluoride) (PVDF)-blend (designated CF)-based nanocomposites. Additionally, organo-montmorillonite (15A) was incorporated simultaneously with the individual carbon fillers to form hybrid filler nanocomposites. Microscopic images confirmed the selective localization of carbon fillers, mainly in the continuous PC phase, while 15A located in the PVDF domains. Differential scanning calorimetry results showed that blending PVDF with PC or forming single/double carbon filler composites resulted in lower PVDF crystallization temperature during cooling. However, PVDF crystallization was promoted by the inclusion of 15A, and the growth of ß-form crystals was induced. The rigidity of the CF blend increased after the formation of nanocomposites. Among the three individually added carbon fillers, GnPs improved the CF moduli the most; the simultaneous loading of CNT/GnP resulted in the highest moduli by up to 33%/46% increases in tensile/flexural moduli, respectively, compared with those of the CF blend. Rheological viscosity results showed that adding CNTs increased the complex viscosity of the blend to a greater extent than did adding CB or GnPs, and the viscosity further increased after adding 15A. The electrical resistivity of the blend decreased with the inclusion of carbon fillers, particularly with CNT loading.

Chitosan/boron nitride nanobiocomposite films with improved properties for active food packaging applications.

Chitosan (CS)/boron nitride nanoplatelet (BNNP) nanobiocomposite films were successfully prepared. Morphological results showed good dispersion of BNNPs in the CS matrix. After loading with BNNPs, water solubility (WS) and moisture absorption of the CS film decreased. The WS decreased from 41.2 to 27.8% at 7 wt% BNNP loading. Additionally, water vapor permeation decreased from 4.2 × 10-11 for pure CS film to 2.9 × 10-11 g m-1s-1Pa-1 at 7 wt% BNNP inclusion. The oxygen permeability of CS film decreased by up to 84% at 7 wt% BNNP loading. The composites showed better sodium hydroxide resistance compared with pure CS. Thermal stability of the composites was higher than the pure CS, up to 35 °C increase at 7 wt% BNNP loading. The addition of 5 wt% BNNPs improved Young's modulus by up to 45% compared with pure CS film. Cytotoxicity of the films decreased after loading with BNNPs.

Cellulose Nanocrystal Reinforced Chitosan Based UV Barrier Composite Films for Sustainable Packaging.

In this study, green composite films based on cellulose nanocrystal/chitosan (CNC/CS) were fabricated by solution casting. FTIR, XRD, SEM, and TEM characterizations were conducted to determine the structure and morphology of the prepared films. The addition of only 4 wt.% CNC in the CS film improved the tensile strength and Young's modulus by up to 39% and 78%, respectively. Depending on CNC content, the moisture absorption decreased by 34.1-24.2% and the water solubility decreased by 35.7-26.5% for the composite films compared with neat CS film. The water vapor permeation decreased from 3.83 × 10-11 to 2.41 × 10-11 gm-1 s-1Pa-1 in the CS-based films loaded with (0-8 wt.%) CNC. The water and UV barrier properties of the composite films showed better performance than those of neat CS film. Results suggested that CNC/CS nanocomposite films can be used as a sustainable packaging material in the food industry.

Polyamide 6/Poly(vinylidene fluoride) Blend-Based Nanocomposites with Enhanced Rigidity: Selective Localization of Carbon Nanotube and Organoclay.

Polyamide 6 (PA6)/poly(vinylidene fluoride) (PVDF) blend-based nanocomposites were successfully prepared using a twin screw extruder. Carbon nanotube (CNT) and organo-montmorillonite (30B) were used individually and simultaneously as reinforcing nanofillers for the immiscible PA6/PVDF blend. Scanning electron micrographs showed that adding 30B reduced the dispersed domain size of PVDF in the blend, and CNT played a vital role in the formation of a quasi-co-continuous PA6-PVDF morphology. Transmission electron microscopy observation revealed that both fillers were mainly located in the PA6 matrix phase. X-ray diffraction patterns showed that the presence of 30B facilitated the formation of γ-form PA6 crystals in the composites. Differential scanning calorimetry results indicated that the crystallization temperature of PA6 increased after adding CNT into the blend. The inclusion of 30B retarded PA6 nucleation (γ-form crystals growth) upon crystallization. The Young's and flexural moduli of the blend increased after adding CNT and/or 30B. 30B exhibited higher enhancing efficiency compared with CNT. The composite with 2 phr 30B exhibited 21% higher Young's modulus than the blend. Measurements of the rheological properties confirmed the development of a pseudo-network structure in the CNT-loaded composites. Double percolation morphology in the PA6/PVDF blend was achieved with the addition of CNT.

Fabrication of Cellulose Nanocrystal/Silver/Alginate Bionanocomposite Films with Enhanced Mechanical and Barrier Properties for Food Packaging Application.

Eco-friendly cellulose nanocrystal/silver/alginate (CNC/Ag/Alg) bionanocomposite films were successfully prepared by blending of CNC with Ag/Alg solution. The CNC was fabricated from cellulose microcrystal (CMC) by acid hydrolysis method. The Ag nanoparticles (AgNPs) were generated by using Alg as a reducing agent through hydrothermal process. AgNPs-included composite films showed characteristic plasmonic effect of the AgNPs with the maximum absorption at 491 nm and they also showed high ultraviolet (UV) barrier properties. The CNC/Ag/Alg composite films were analyzed by using scanning electron microscopy, transmission electron microscopy, optical microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction technique. Depending on the type of nanofillers, tensile strength of the composite films increased by 39-57% and water vapor permeation decreased by 17-36% compared with those of the neat Alg films. The Ag/Alg and CNC/Ag/Alg films showed brown color as detected from the increase of both 'b' and 'a' parameters by colorimeter. The UV and water barrier properties of Alg based composite films were found higher than the Alg films. The obtained results suggested that the prepared composite films can be used in food packaging applications.

Graphene Nanoplatelet-Reinforced Poly(vinylidene fluoride)/High Density Polyethylene Blend-Based Nanocomposites with Enhanced Thermal and Electrical Properties.

In this study, a graphene nanoplatelet (GNP) was used as a reinforcing filler to prepare poly(vinylidene fluoride) (PVDF)/high density polyethylene (HDPE) blend-based nanocomposites through a melt mixing method. Scanning electron microscopy confirmed that the GNP was mainly distributed within the PVDF matrix phase. X-ray diffraction analysis showed that PVDF and HDPE retained their crystal structure in the blend and composites. Thermogravimetric analysis showed that the addition of GNP enhanced the thermal stability of the blend, which was more evident in a nitrogen environment than in an air environment. Differential scanning calorimetry results showed that GNP facilitated the nucleation of PVDF and HDPE in the composites upon crystallization. The activation energy for non-isothermal crystallization of PVDF increased with increasing GNP loading in the composites. The Avrami n values ranged from 1.9⁻3.8 for isothermal crystallization of PVDF in different samples. The Young's and flexural moduli of the blend improved by more than 20% at 2 phr GNP loading in the composites. The measured rheological properties confirmed the formation of a pseudo-network structure of GNP-PVDF in the composites. The electrical resistivity of the blend reduced by three orders at a 3-phr GNP loading. The PVDF/HDPE blend and composites showed interesting application prospects for electromechanical devices and capacitors.

Cellulose nanocrystals reinforced κ-carrageenan based UV resistant transparent bionanocomposite films for sustainable packaging applications.

In this work, κ-carrageenan bionanocomposite films were prepared by solution casting of a mixture of κ-carrageenan, glycerol, and various amounts of cellulose nanocrystals (CNCs, 0-9 wt.%). The structure and morphology of the bionanocomposite films were characterized by Fourier-transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, and scanning electron microscopy. Compared with κ-carrageenan films, the κ-carrageenan bionanocomposite films showed better mechanical and barrier properties (water and UV) and thermal stability. The water contact angle increased from 23.30° to 71.80° and the water vapor permeation decreased from 8.93 gm-1 s-1 Pa-1 to 4.69 × 10-11 gm-1 s-1 Pa-1 in the κ-carrageenan films loaded with 9-7 wt.% CNCs, respectively. The tensile strength and elongation at break of the films increased from 38.33 ± 3.79 MPa to 52.73 ± 0.70 MPa and from 21.50 ± 3.72% to 28.27 ± 2.39%, respectively, after CNC loading increased from 0 wt.% to 7.0 wt.%. These results indicated that the κ-carrageenan nanocomposite films have potential applications in food packaging.