The fabrication of flexible and oxygen barrier cellulose nanofiber/polylactic acid nanocomposites using cosolvent system

The main disadvantages of polylactic acid (PLA) for food packaging applications are its brittleness and poor gas barrier properties. The purpose of this study is to evaluate the potential usability of triethyl citrate (TEC) and cellulose nanofiber (CNF) in PLA to obtain bio-based films with optimal properties. The incorporation of CNF as reinforcement fillers in polymer matrix has long been debated due to its difficulties to disperse uniformly in hydrophobic polymer matrix attribute to their hydrophobic nature. In order to overcome this problem, different feeding method for CNF into the mixer was studied, and CNF/PLA nanocomposites were characterized. It was found that CNF was successfully dispersed in the PLA matrix through the TEC-CNF suspension, which greatly improved tensile strength and flexibility of the CNF/PLA nanocomposites. The oxygen barrier property was enhanced up to 47.3% (16.99 cc·mm/m²·day·atm) with the increase loading of 0.25, 0.50, and 1 wt% of CNF. Moreover, the dynamic mechanical analysis showed that the low tan delta peak of CNF/PLA nanocomposites (48.25°C) was shifted to high peak (52.99°C) due to incorporation of TEC; indicates an improved of thermal stability of the composites. Overall, the t-CNF/PLA nanocomposites show a great feasibility for various eco-friendly flexible packaging applications.     

Studies of polylactide/zinc oxide nanocomposites: influence of surface treatment on zinc oxide antibacterial activities in textile nanocomposites

Polylactide (PLA)/zinc oxide (ZnO) nanocomposite filaments were produced with a melt‐spinning process, with the aim of obtaining antibacterial textiles. ZnO, an inorganic antibacterial nanofiller, is used to impart antibacterial properties to PLA. These nanoparticles suit the melt‐spinning process because of their high thermal stability and low granulometry. Generally, metallic oxides (e.g., ZnO) are used to recycle PLA via catalyzed unzipping depolymerization. In this study, we used different ways to finely disperse ZnO in PLA and produce filaments with a minimum degradation of the thermal and mechanical properties. Optimized antibacterial properties were obtained with a fabric containing ZnO with specific surface treatments. The reasons for this better antibacterial activity, related to the study of the antibacterial mechanism of ZnO, were investigated with different characterization techniques [X‐ray, electron probe microanalysis, inductively coupled plasma mass spectrometry, and electron paramagnetic resonance (EPR)]. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41776.     

Current application of controlled degradation processes in polymer modification and functionalization

Ecological concerns over the accumulation of polymeric waste material and the demand for functionalized polymers in specialty applications have promoted extensive research on different controlled degradation processes and their use. The production of functionalized or modified polymers by conventional synthetic routes is expensive and time consuming. However, advances in degradation technology have become an enabling factor in the production of modified polymers and their functionalization. Mild irradiation, ozonization, and enzymatic routes are among the processes that have been explored for polymer modification. Biopolymers, such as chitosan, hyaluronic acids, and polyhydroxyalkanoates, are known to be suitable for a diverse number of applications, ranging from biomedical to organic‐electronics. At the same time, their high molecular weight, crystallinity, and shelf degradability limit their utility. Controlled degradation processes can be used to prepare these types of polymers with reasonably low molecular weights and to generate radical species that help to stabilize these polymers or to initiate further beneficial reactions. In this article, we review the application of controlled degradation processes for polymer modification and functionalization. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effectiveness of the preparation of maleic anhydride grafted poly (lactic acid) by reactive processing for poly (lactic acid)/carbon nanotubes nanocomposites

An effective strategy to increase the properties of poly (lactic acid) (PLA) is the addition of carbon nanotubes (CNT). In this work, aiming to improve the surface adhesion of PLA and CNT a new compatibilizer agent was prepared by reactive processing, PLA grafted maleic anhydride (PLA-g-MA) using benzoyl peroxide and maleic anhydride. The effectiveness of the PLA-g-MA as a compatibilizer agent was verified for PLA/PLA-g-MA/CNT nanocomposites. PLA and PLA-g-MA samples were characterized by Fourier transform infrared spectroscopy (FT-IR) to confirm the grafting reaction of maleic anhydride on PLA chains and by rheological analysis to prove the changes in the matrix PLA after the graphitization reaction. Thermal (differential scanning calorimetry and thermogravimetric analysis), mechanical tests (Izod impact strength and tensile test), and morphological characterization were used to verify the effect of the compatibilizer agent. The preparation of PLA-g-MA by reactive extrusion processing proved satisfactory and the nanocomposites presented good thermal and mechanical properties. The addition of the PLA-g-MA also contributed to the greater distribution of CNT and can be used as an alternative for the production of PLA/CNT nanocomposites.     

Chitosan/MCM‐41 nanocomposites for efficient beryllium separation

Chitosan nanoparticles (Ch NPs) with individual particles 10–30 nm in size and average aggregate sizes of 240 nm were prepared via ionic gelation. Ordered mesoporous Mobil Composition of Matter No. 41 (MCM‐41) with a surface area of 1590 m²/g was prepared via a sol–gel method. The nanocomposites were prepared via the in situ dispersion of MCM‐41 in chitosan followed by ionic gelation with a multivalent anion to produce MCM‐41‐impregnated Ch NPs or via the mixture of dispersed MCM‐41 with preprepared Ch NPs to produce Ch NPs supported on MCM‐41. The beryllium‐uptake efficiency was studied with different pH values, contact times, and initial Be(II) concentrations. The maximum achieved uptake efficiencies of the nanocomposites (95% and 96%) were superior to that of MCM‐41 (38%) and higher than that of Ch NPs (90%). The nanocomposite formulas facilitated post‐treatment separation while maintaining a high beryllium‐uptake efficiency. The Be(II)‐uptake process for all of the materials followed the pseudo‐second‐order kinetic model and both the Langmuir and Freundlich isotherms. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46040.     

PBAT/TPS-nanowhiskers blends preparation and application as food packaging

About 85–90% of the market for new materials in biodegradable packaging is served by various blends and composites containing starch in some portion. In an attempt to satisfy the increasing consumer demand, innovative materials are being developed. This includes the concept of active packaging, which, in addition to protecting, interacts with the packaged product. In this context, flexible films have been prepared from blends of poly(butylene adipate-co-terephthalate), thermoplastic starch (TPS), and cellulose nanowhiskers (CNW) at different concentrations (0–3.0 wt %) and with distinct compatibilizing agents (glycerol, stearic acid, and citric acid) by flat extrusion. Palm oil was packaged in the films, and was stored under accelerated oxidation conditions as a model system. The films were also used for packing lettuce. The TPS increased the rate of water vapor permeability of the blends. The micrographs showed the films with very porous surface as a function of the CNW concentration. In addition to the antimicrobial action pronounced within 10 days (fungi—molds and yeasts; bacteria—mesophilic and psychrotrophic), the film showed a prooxidant action, indicating its suitability for fruit and vegetable packaging. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47699.     

PLA/sepiolite and PLA/calcium carbonate nanocomposites: A comparison study

Polylactic acid (PLA)‐based nanocomposites comprising two different types of nanofillers, i.e. sepiolite (SEP) and nano calcium carbonate (NCC), were prepared by internal mixing and injection molding. Because of the different aspect ratio, surface area, and surface property of the nanofillers, their effects on the morphological, mechanical, dynamic mechanical, rheological, and thermal properties of the nanocomposites were shown to be very different. NCC demonstrated more uniform particle dispersion and matrix compatibility than did SEP because of the former's surface treatment, thus leading to higher strength and strain‐at‐failure of PLA/NCC composites. On the other hand, larger aspect ratio and surface area of SEP caused higher melt viscosity, stronger shear thinning, and better thermal resistance of PLA/SEP composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of polyimide/polyhedral oligomeric silsesquioxane nanocomposites containing quinolyl moiety

A series of functional polyhedral oligomeric silsesquioxane (POSS)/polyimide (PI) nanocomposites were prepared using a two‐step approach. First, octa(aminophenyl)silsesquioxane (OAPS) was mixed with poly(amic acid) (PAA) prepared by reacting bis(4‐amino‐3,5‐dimethylphenyl)‐3‐quinolylmethane and 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride. Second, the resulting solution was subjected to thermal imidization. The well‐defined ‘hard particles’ (POSS) and the strong covalent bonds in the amide linkage between the carbon atom of the carboxyl side group in PAA and the nitrogen atom of the amino group in POSS lead to a significant improvement in the thermal and mechanical properties. Homogeneous dispersion of POSS cages in the PI is evident from scanning electron microscopy, which further confirms that the POSS molecule becomes an integral part of the organic‐inorganic inter‐crosslinked network system. Differential scanning calorimetry and dynamic mechanical analysis show that the glass transition temperatures of the POSS‐containing nanocomposites are higher than that of the corresponding neat PI system, owing to the significant increase of the crosslinking density in the PI/POSS nanocomposites. Increasing the concentration of OAPS in the PI networks decreases the dielectric constant. Pure PI and PI/POSS systems have good antimicrobial activity. Copyright © 2011 Society of Chemical Industry     

Polyimide and polyhedral oligomeric silsesquioxane nanocomposites for low-dielectric applications

A novel polyimide (PI) hybrid nanocomposite containing polyhedral oligomeric silsesquioxane (POSS) with well defined architecture has been prepared by copolymerization of octakis(glycidyldimethylsiloxy)octasilsesquioxane (Epoxy-POSS), 4,4′-oxydianiline diamine (ODA), and 4,4′-carbonyldiphthalic anhydride (BTDA). In these nanocomposite materials, the equivalent ratio of the Epoxy-POSS and ODA are adjustable, and the resultant PI-POSS nanocomposites give variable thermal and mechanical properties. More importantly, we intend to explore the possibility of incorporating POSS moiety through the Epoxy-POSS into the polyimide network to achieve the polyimide hybrid with lower dielectric constant (low-k) and thermal expansion. The lowest dielectric constant achieved of the POSS/PI material (PI-10P) is 2.65 by incorporating 10 wt% Epoxy-POSS (pure PI, k=3.22). In addition, when contents of the POSS in the hybrids are 0, 3, 10 wt% (PI-0P, PI-3P, PI-10P), and the resultant thermal expansion coefficients (TEC) are 66.23, 63.28, and 58.25 ppm/°C, respectively. The reduction in the dielectric constants and the resultant thermal expansion coefficients of the PI-POSS hybrids can be explained in terms of creating silsesquioxane cores of the POSS and the free volume increase by the presence of the POSS-tethers network resulting in a loose PI structure.     

Biodegradable polypropylene/thermoplastic starch nanocomposites incorporating halloysite nanotubes

In this work, polypropylene/thermoplastic starch (PP/TPS) with and without halloysite nanotubes (HNTs) was prepared via melt mixing in order to obtain environmentally friendly plastics. PP‐grafted maleic anhydride (PP‐g‐MA) was used to improve the compatibility among the highly incompatible polymers. The mechanical characterization showed a reduction in the tensile properties of the polymer when TPS increased; however, HNT successfully compensated for some of the observed losses. The results from the thermogravimetric analysis (TGA) indicated that HNT is an efficient reinforcement for the thermal stability improvement. TPS caused an increase in the storage modulus (G′) and the complex viscosity (η*) which marks a change in the viscoelastic properties of the system. The scanning electron microscope (SEM) images showed the effective plasticization of starch and better dispersion of TPS in the presence of HNT. Some samples were also buried in the soil to measure their sustainability after their lifetime lapse. The results indicated that TPS improves the biodegradability of the PP/TPS system. PP considerably lowered the moisture uptake of TPS; nevertheless, HNT caused a slight increase in the moisture absorption. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45740.     

Effects of GPTMS concentration and powder to liquid ratio on the flowability and biodegradation behaviors of 45S5 bioglass/tragacanth bioactive composite pastes

Injectable composite pastes were prepared using melt-derived 45S5 bioactive glass and tragacanth crosslinked by (3-glycidyloxypropyl)trimethoxysilane (GPTMS). The effect of powder to liquid ratio (P:L = 1.0:2.0–1.0:2.5) and GPTMS/tragacanth ratio (0.0–1.5) on the injectability, swelling behavior, rheology, bioactivity, and cellular behavior of the pastes was investigated. Based on the results, the apparent stability and consistency of the pastes increased upon crosslinking by GPTMS. Due to the increased interactions between tragacanth and glass, a hysteresis loop with larger area was formed in the presence of GPTMS. With increase of GPTMS:tragacanth ratio from 0 to 1.5, the swelling percent dropped from 24.65 to 16.25% after 24 h and the degradation percent also went down from 27.89 to 9.11% after 21 days in the simulated body fluid. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay showed a drop in the optical density of MG63 osteoblasts up to 30.07% after exposure to the GPTMS-crosslinked composite pastes for 3 days. However, the number of viable cells gradually increased in the presence of the pastes and the cell morphology remained unchanged over time. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47604.     

Cellulose acetate ultrafiltration membranes reinforced by cellulose nanocrystals: Preparation and characterization

Cellulose nanocrystals (CNCs) were used as a sustainable additive to improve the hydrophilicity, permeability, antifouling, and mechanical properties of blend membranes. Different CNC loadings (0–1.2 wt %) in cellulose acetate (CA) membranes were studied. The blend membranes were prepared by a phase‐inversion process, and their chemical structure and morphological properties were characterized by attenuated total reflectance–Fourier transform infrared spectroscopy, scanning electron microscopy, porosity, and mean pore size and contact angle measurement. The blend membranes became more porous and more interconnected after the addition of CNCs. The thickness of the top layer decreased and a few large holes in the porous substrate appeared with increasing CNC loading. In comparison with the pure CA membranes, the pure water flux of the blend membranes increased with increasing CNC loading. It reaches a maximum value of 76 L m^?2 h^?1 when the CNC loading was 0.5 wt %. The antifouling properties of the CA membrane were significantly improved after the addition of CNCs, and the flux recovery ratio value increased to 68% with the addition of 0.5 wt % CNCs. In comparison with that of the pure CA membranes, the tensile strength of the composite membranes increased by 47%. This study demonstrated the importance of using sustainable CNCs to achieve great improvements in the physical and chemical performance of CA ultrafiltration membranes and provided an efficient method for preparing high‐performance membranes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43946.     

Self‐driven graft polymerization of vinyl monomers on poultry chicken feathers in the absence of initiator/catalyst

An efficient and simple method for graft copolymerization of powdered chicken feather (CF) with vinyl monomers without any free radical initiator is reported. Various vinyl monomers such as glycidyl methacrylate (GMA), styrene (S), and methyl methacrylate (MMA); (20–60 wt % with respect to CF) were successfully grafted to chicken feather (CF) by using sodium dodecyl sulfate (SDS, 0.086–0.5 mmol) in the absence of any catalyst or initiator. Most likely, the hydrophilicity, hydrophobicity, and complex forming properties of chicken feather keratin with surfactant molecules were responsible for efficient grafting of polymers on CF surface. The effect of polymerization conditions, such as monomer concentration, temperature, and time of reaction, on the grafting parameters such as monomer conversion, grafting efficiency, and molar grafting ratio were studied. The described method showed a good potential of using low cost, easily accessible poultry chicken feathers as grafting material and self catalyzing agent for graft copolymerization with vinyl monomers to produce low cost commodity plastic for various end uses. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44645.     

Montmorillonite reinforced type A gelatin nanocomposites

This study investigates the structural, morphological, thermal, and mechanical properties of type A gelatin/montmorillonite (MMT) films as a function of MMT concentration. The variations of the X‐ray diffraction pattern suggest that the structure of the nanocomposites turns from intercalated to exfoliated on increasing clay loading up to 20 wt %. Simultaneously, gelatin interaction with clay negative sheets during gelling provokes a reduction of the triple helix content of the composite films, in agreement with the reduction of the relative intensity of the 1.1 nm diffraction reflection of gelatin and of the values of denaturation enthalpy. On the other hand, the increase of the denaturation and decomposition temperatures, the significant rise of the Young's modulus, as well as the swelling decrease observed as clay content increases, demonstrate a relevant stabilizing effect of MMT on gelatin. The reinforcement action of MMT allows to utilize a relatively low concentration of the crosslinking agent genipin to further stabilize the films. The synergic action of clay and genipin prevents dissolution of the nanocomposites in aqueous solution and enhances their mechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40301.     

Green synthesis and characterization of poly(glycerol-azelaic acid) and its nanocomposites for applications in regenerative medicine

A series of novel bio-polyester nanocomposites based on glycerin and azelaic acid as monomers incorporating hydroxyapatite (HA) nanoparticles were fabricated via in situ polymerization method. Chemical structure of the samples was investigated by ¹H-NMR, ¹³C-NMR, and Fourier-transform infrared spectroscopy (FTIR). Energy dispersive X-ray-mapping analysis illustrated that the nanoparticles were well dispersed in the poly (glycerol azelaic acid) (PGAZ) matrix. Viscoelastic properties of the samples under various frequencies were examined in which the PGAZ specimen containing 1.0 wt% of HA nanoparticles (PGAZH1.0) exhibited superlative properties. Furthermore, the alterations in the glass transition temperature of the samples were comprehensively discussed. Thermal gravimetric analysis displayed that nanocomposites generally have a difference in degradation patterns from that of the pristine sample. Dynamic contact angle demonstrated that the presence of HA nanoparticles imposed a significant influence on hydrophilicity. The hydrolytic degradation values at pH = 7 and pH = 11 were measured and determined that the degradation rate for the PGAZ sample containing 1.5 wt% HA (PGAZH1.5) was higher than those of the other samples. Moreover, in vitro studies elucidated that cell attachment on PGAZH1.0 and PAZH1.5 surfaces were acceptable.     

Crystallization behavior of ultrahigh‐molecular‐weight polyethylene/polyhedral oligomeric silsesquioxane nanocomposites prepared by ethylene in situ polymerization

A [3‐t‐Bu‐2‐O? C₆H₃CH?N(C₆F₅)]₂TiCl₂ catalyst (bis(phenoxyimine)titanium dichloride complex – FI catalyst) was immobilized on disilanolisobutyl polyhedral oligomeric silsesquioxane (OH‐POSS) to prepare ultrahigh molecular‐weight polyethylene (UHMWPE)/polyhedral oligomeric silsesquioxane (POSS) nanocomposites during ethylene in situ polymerization. The dispersion state of POSS in the UHMWPE matrix was characterized by X‐ray diffraction measurements and transmission electron microscopy. It was shown that the OH‐POSS achieved uniformed dispersion in the UHMWPE matrix, although its polarity was unmatched. The isothermal and nonisothermal crystallization behavior of the nanocomposites was investigated by means of differential scanning calorimetry. The crystallization rate of the nanocomposites was enhanced because of the incorporation of POSS during the isothermal crystallization. POSS acted as a nucleus for the initial nucleation and the subsequent growth of the crystallites. For nonisothermal studies, POSS showed an increase in the crystallinity. The crystallization rate of the nanocomposites decreased because the presence of POSS hindered the crystal growth. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40847.     

Analyzing the interactions and miscibility of silk fibroin/mucin blends

Mucin, a glycoprotein with viscoelastic properties, and silk fibroin, a protein excreted from silkworms with properties of thermal and mechanical resistance, have been probed as building blocks in the design of biomaterials. Aiming to evaluate the interaction and miscibility between mucin and fibroin, we synthesized silk fibroin and mucin (SF/MU) blends for biomedical applications. The morphological analysis of the SF/MU blends showed the presence of two phases, suggesting a partial miscibility between the polymers. The degradation temperature of the SF/MU blends increased with an increase in the silk fibroin content, indicating that silk fibroin contributed to the thermal stability of the blends. The glass transition temperature of the SF/MU blends lay between the values of the pure polymers. The Fourier-transform infrared spectroscopy results pointed out that the interaction between fibroin and mucin occurred between the amine group of silk fibroin and mucin carboxyl and hydroxyl groups. The outcomes of this work provided essential information on the miscibility of the SF/MU blends. These findings will be critical for further studies with fibroin and mucin-based biomaterials, especially in mucoadhesive systems and wound healing applications.     

Mechanical,thermal, and barrier properties of nanocomposites based on poly(butylene succinate)/thermoplastic starch blends containing different types of clay

Nanocomposites based on blends of poly(butylene succinate) (PBS) and thermoplastic cassava starch (TPS) were prepared using a two‐roll mill and compression molding, respectively. Two different types of clay, namely sodium montmorillonite (CloisiteNa) and the organo‐modified MMT (Cloisite30B) were used. The morphological and mechanical properties of the nanocomposite materials were determined by using XRD technique and a tensile test, respectively. Thermal properties of the composite were also examined by dynamic mechanical thermal analysis and thermal gravimetric techniques. Barrier properties of the nanocomposites were determined using oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) tests. From the results, it was found that by adding 5 pph of the clay, the tensile modulus and the thermal properties of the blend containing high TPS (75 wt %) changed significantly. The effects were also dependent on the type of clay used. The use of Cloisite30B led to a nanocomposite with a higher tensile modulus value, whereas the use of CloisiteNa slightly enhanced the thermal stability of the material. OTR and WVTR values of the blend composites containing high PBS ratio (75 wt %) also decreased when compared to those of the neat PBS/TPS blend. XRD patterns of the nanocomposites suggested some intercalation and exfoliation of the clays in the polymer matrix. The above effects are discussed in the light of different interaction between clays and the polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1114‐1123, 2013     

Preparation and application of magnetic chitosan in environmental remediation and other fields: A review

Magnetic chitosan has received considerable attention over the decades due to its low cost, biodegradability, green sources, magnetic intensity. In this review, we reviewed the preparation methods of magnetic chitosan using co-precipitation, cross-linking and electrochemical. Therein cross-linking methodologies involved in the reaction of amino groups are facile to introduce additional reaction groups and improve anti-swelling of chitosan layers, mostly in an acidic environment. Besides, we focused on the applications of magnetic chitosan in various fields such as wastewater treatment, for example, removal of heavy metal ions, organic/inorganic dyes, fluorides, and pesticides. Moreover, magnetic chitosan also reveals great potential application in the field of medical, pharmaceutical, food and electronic screening. Above all, magnetic chitosan is economically and operationally beneficial as it can be easily separated and controlled with an external magnetic field and can be modified to maximize its functions.     

Transparent low‐density polyethylene/starch nanocomposite films

Low‐density polyethylene (LDPE)/starch nanocomposite films were prepared by melt extrusion process. The first step includes the preparation of starch–clay nanocomposite by solution intercalation method. The resultant product was then melt mixed with the main matrix, which is LDPE. Maleic anhydride‐grafted polyethylene (MAgPE), produced by reactive extrusion, was used as a compatibilizer between starch and LDPE phases. The effects of using compatibilizer, clay, and plasticizers on physico‐mechanical properties were investigated. The results indicated that the initial intercalation reaction of clay layers with starch molecules, the conversion of starch into thermoplastic starch (TPS) by plasticizers, and using MAgPE as a compatibilizer provided uniform distribution of both starch particles and clay layers, without any need of alkyl ammonium treatment, in LDPE matrix. The nanocomposite films exhibited better tensile properties compared to clay‐free ones. In addition, the transparency of LDPE film did not significantly change in the presence of TPS and clay particles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013