Preparation and properties of poly(propylene carbonate) and nanosized ZnO composite films for packaging applications

A series of polypropylene carbonate (PPC)/ZnO nanocomposite films with different ZnO contents were prepared via a solution blending method. The morphological structures, thermal properties, oxygen permeability, water sorption, and antibacterial properties of the films were investigated as a function of ZnO concentration. While all of the composite films with less than 5 wt % ZnO exhibited good dispersion of ZnO in the PPC matrix, FTIR and SEM results revealed that solution blending did not lead to a strong interaction between PPC and unmodified ZnO. As such, poor dispersion was induced in the composite films with a high ZnO content. By incorporating inorganic ZnO filler nanoparticles, the diffusion coefficient, water uptake in equilibrium, and oxygen permeability decreased as the content of ZnO increased. The PPC/ZnO nanocomposite films also displayed a good inhibitory effect on the growth of bacteria in the antimicrobial analysis. The enhancement in the physical properties achieved by incorporating ZnO is advantageous in packaging applications, where antimicrobial and environmental‐friendly properties, as well as good water and oxygen barrier characteristics are required. Furthermore, UV light below ～ 350 nm can be efficiently absorbed by incorporating ZnO nanoparticles into a PPC matrix. ZnO nanoparticles can also improve the weatherability of a PPC film. In future research, the compatibility and dispersion of the PPC matrix polymer and the inorganic ZnO filler nanoparticles should be increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Effects of ZnO nanoparticles on the mechanical and antibacterial properties of polyurethane coatings

Polyurethane-based coatings reinforced by ZnO nanoparticles (about 27 nm) were prepared via solution blending. The ZnO/PU films and coats were fabricated by a simple method of solution casting and evaporation. The mechanical properties of the films were investigated by a universal material test, and the abrasion resistance of the prepared coats was evaluated by a pencil-abrasion-resistance tester. It was found that significant improvement of the PU films in Young’s modulus and tensile strength was achieved by incorporating ZnO nanoparticles up to 2.0 wt%, and that the abrasion resistance of the PU coats was greatly enhanced due to the addition of ZnO nanoparticles. Moreover, the antibacterial property test was carried out via the agar dilution method and the result indicated that PU films doped with ZnO nanoparticles showed excellent antibacterial activity, especially for Escherichia coli.     

Preparation and properties of hydrophobic layered silicate-reinforced UV-curable poly(urethane acrylate) nanocomposite films for packaging applications

A series of poly(urethane acrylate)/Cloisite 15A (PUA/C15A) nanocomposite films were successfully prepared via a UV-curing system, and their physical and barrier properties were investigated as a function of clay content. The physical properties were strongly dependent upon the chemical and morphological structures originating from differences in Cloisite 15A content. With high clay content, the PUA/C15A nanocomposite films displayed an intercalation/exfoliation combined structure. However, no strong interfacial interactions occurred between the PUA and clay, possibly leading to poor dispersion with relatively high clay content. The thermal stability displayed some enhancement with the introduction of clay into PUA, while the gas and moisture barrier properties showed significant enhancement. The oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) decreased with increasing contents of Cloisite 15A, and varied within the range of 714.0–71.1 cm³/m² day and 29.9–13.9 g/m² day, respectively. Thus the enhanced gas and moisture barrier properties of PUA/C15A nanocomposite films make them promising candidates for food and pharmaceutical packaging applications. However, further studies will be performed to increase the compatibility and dispersion of clay particles in the PUA polymer matrix.     

Preparation and characterization of UV‐curable ZnO/polymer nanocomposite films

A series of novel nano‐ZnO/polymer composite films with different ZnO contents was prepared through incorporation of pre‐made colloidal ZnO particles into monomer mixtures of urethane‐methacrylate oligomer and 2‐hydroxyethyl methacrylate, followed by ultraviolet (UV) radiation‐initiated polymerization. The colloidal ZnO nanoparticles with a diameter of 3–5 nm were synthesized from zinc acetate and lithium hydroxide in ethanol via a wet chemical method. In order to stabilize and immobilize the ZnO particles into the polymer matrix, the ZnO nanoparticles were further capped using 3‐(trimethoxysilyl)propyl methacrylate. Thermogravimetric analyses show that the ZnO nanoparticles were successfully incorporated into the polymer matrix and these ZnO/polymer composites have a good thermal stability. Transmission electron microscopy studies indicate the ZnO nanoparticles were uniformly dispersed in the polymer and they remained at the original size (3–5 nm) before immobilization. All nanocomposite films with ZnO particle contents from 1 to 15 wt% show good transparency in the visible region and luminescent properties. In addition, composite films with high ZnO content (>7 wt%) are able to absorb UV irradiation below 350 nm, indicating that these composite films exhibit good UV screening effects. Copyright © 2006 Society of Chemical Industry     

Transparent and thermally stable improved poly (vinyl alcohol)/Cloisite Na/ZnO hybrid nanocomposite films: Fabrication,morphology and surface properties

A series of poly(vinyl alcohol)/Cloisite Na⁺-Tyrosine/Zinc oxide (PVA/Cloisite Na⁺-Tyr/ZnO) bionanocomposites were prepared by dispersing ZnO nanoparticles in solution containing mixture of the PVA and modified Cloisite Na⁺. Structure of nanocomposite coatings was investigated by X-ray diffraction and Fourier-transform infrared spectroscopy. The thermal stability and optical properties of bionanocomposite were characterized by thermogravimetric analysis and UV–vis spectroscopy, respectively. The introduction of ZnO nanoparticles into PVA/Cloisite Na⁺-Tyr mixed solutions significantly increased the thermal stability of the obtained films. The results revealed that the high UV-shielding efficiency of the composites: for a film containing 6.0 wt% of ZnO nanocrystals, over 92% of UV light at wavelengths of 368 nm was absorbed while the optical transparency in the visible region was slightly below that of a PVA/Cloisite Na⁺-Tyr film.     

Preparation and characterizations of highly transparent UV-curable ZnO-acrylic nanocomposites

A sol–gel chemical route was adopted to prepare the zinc oxide (ZnO) nanoparticles as small as 4 nm. UV-curable ZnO-acrylic nanocomposites were then prepared by employing 3-(trimethoxysilyl)propyl methacrylate (TPMA) as the surface modification agent of ZnO particles. UV–vis analysis revealed a high optical transparency (>95%) in visible light region for nanocomposite thin films with ZnO contents up to 20 wt.%. The addition of ZnO nanoparticles also enhanced the dielectric constants of nanocomposites and the dielectric constants greater than 4 in frequencies ranging from 1 to 600 MHz was obtained in the samples containing 10 wt.% of ZnO nanoparticles. A comparison of experimental results and theoretical calculation indicated that the interfacial polarizations in between ZnO nanoparticles and polymer matrix may play an important role in the enhancement of dielectric properties of nanocomposites.     

Mechanical and antibacterial properties of modified nano‐ZnO/high‐density polyethylene composite films with a low doped content of nano‐ZnO

Nano‐ZnO/high‐density polyethylene (HDPE) composite films were prepared via melt blending and a hot compression‐molding process. The properties, including ultraviolet absorption, mechanical and antibacterial properties of the films, and plasticizing behavior of the composites, were investigated. The results show that the absorbance in the ultraviolet region of the HDPE films was enhanced after the addition of modified nano‐ZnO to the HDPE matrix. Also, we found that improvement in the HDPE films of the tensile strength and elongation at break was achieved by the incorporation of modified ZnO nanoparticles up to 0.5 wt % in contrast with the original nano‐ZnO/HDPE composite films. Antibacterial testing was carried out via plate counting, and the results indicate that the HDPE films doped with modified ZnO nanoparticles showed favorable antibacterial activity, especially for Staphylococcus aureus. However, the low doped content of modified nano‐ZnO in the HDPE matrix made the balance torque of the composites increase slightly. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

ZnO nanosphere fabrication using the functionalized polystyrene nanoparticles for dye-sensitized solar cells

The nano-hollow spherical ZnO (NHS ZnO) photoelectrodes were prepared using functionalized polystyrene nanoparticles with flexible dimensional control of the particle diameter for dye-sensitized solar cells applications. NHS ZnO was formed by ZnO nanoparticles that accumulated on the surface of functionalized polystyrene with a high ionic strength. This method represents a one-step preparation method for an inorganic shell via polymerization between ZnO complexes. Even though NHS ZnO has a submicron size, it composed of nanoparticles that connect with each other, thereby implying good electron transfer properties, and has a high surface area. The submicron-sized diameter NHS ZnO has an enhanced light scattering capacity, which promotes the photons with more opportunities to be absorbed by the N719 dye molecules. Therefore, the ZnO films prepared from 600 nm to 1000 nm NHS ZnO possessed higher IPCE values over a wide range (from 400 nm to 750 nm) compared to films of the 300 nm ZnO due to the enhanced light scattering capacities of the film. In photocurrent-voltage measurements, the short-circuit current density of 300 nm and 600 nm NHS ZnO increases from 3.33 mA/cm² to 6.53 mA/cm² while the cell efficiency increases from 1.04% to 3.02% due to the light scattering efficiency. Electrochemical impedance spectroscopy showed that electrons in NHS ZnO with a larger particle size have a longer electron lifetime than NHS ZnO with a smaller particle size, as the latter hinders the electron transport in the NHS ZnO nanostructured films.     

Preparation and characterization of transparent ZnO/epoxy nanocomposites with high-UV shielding efficiency

Transparent ZnO/epoxy nanocomposites with high-UV shielding efficiency were reported in this paper. First, zinc oxide (ZnO) precursor was synthesized via the homogeneous precipitation method and ZnO nanoparticles were then made by calcination of the precursor at different temperature. The structural properties of the as-prepared ZnO nanoparticles were studied in detail using thermogravimetry (TGA), differential thermal analysis (DTA), X-ray diffractometer (XRD), Fourier transform infrared spectrometer (FT-IR) and transmission electron microscopy (TEM), respectively. Transparent ZnO/epoxy nanocomposites were subsequently prepared from transparent epoxy (EP-400) and as-prepared ZnO nanoparticles via in situ polymerization. Optical properties of ZnO/epoxy nanocomposites, namely visible light transparency and UV light shielding efficiency, were studied using an ultraviolet-visible (UV-vis) spectrophotometer. The optical properties of the as-obtained nanocomposites were shown to depend on ZnO particle size and content. The nanocomposite containing a very low content (0.07% in weight) of ZnO nanoparticles with an average particle size of 26.7 nm after calcination at 350 °C possessed the most optimal optical properties, namely high-visible light transparency and high-UV light shielding efficiency, that are desirable for many important applications.     

Cellulose Nanocrystals/ZnO as a Bifunctional Reinforcing Nanocomposite for Poly(vinyl alcohol)/Chitosan Blend Films: Fabrication,Characterization and Properties

In this study, cellulose nanocrystals/zinc oxide (CNCs/ZnO) nanocomposites were dispersed as bifunctional nano-sized fillers into poly(vinyl alcohol) (PVA) and chitosan (Cs) blend by a solvent casting method to prepare PVA/Cs/CNCs/ZnO bio-nanocomposites films. The morphology, thermal, mechanical and UV-vis absorption properties, as well antimicrobial effects of the bio-nanocomposite films were investigated. It demonstrated that CNCs/ZnO were compatible with PVA/Cs and dispersed homogeneously in the polymer blend matrix. CNCs/ZnO improved tensile strength and modulus of PVA/Cs significantly. Tensile strength and modulus of bio-nanocomposite films increased from 55.0 to 153.2 MPa and from 395 to 932 MPa, respectively with increasing nano-sized filler amount from 0 to 5.0 wt %. The thermal stability of PVA/Cs was also enhanced at 1.0 wt % CNCs/ZnO loading. UV light can be efficiently absorbed by incorporating ZnO nanoparticles into a PVA/Cs matrix, signifying that these bio-nanocomposite films show good UV-shielding effects. Moreover, the biocomposites films showed antibacterial activity toward the bacterial species Salmonella choleraesuis and Staphylococcus aureus. The improved physical properties obtained by incorporating CNCs/ZnO can be useful in variety uses.     

Preparation and properties of poly(urethane acrylate) (PUA) and tetrapod ZnO whisker (TZnO‐W) composite films

Tetrapod zinc oxide whiskers (TZnO‐Ws) were successfully synthesized via a thermal oxidation method and confirmed using Fourier transform infrared spectroscopy, X‐ray diffraction and scanning electron microscopy. A series of poly(urethane acrylate) (PUA)/TZnO‐W composite films with various TZnO‐W contents were prepared via a UV curing method and their physical properties were investigated to understand their possible use as packaging materials. The morphological, thermal, mechanical, antibacterial and barrier properties of the PUA/TZnO‐W composite films were interpreted as a function of TZnO‐W content. The thermal stability, barrier properties and antibacterial properties of the composite films, which were strongly dependent upon their chemical and morphological structure, were enhanced as the TZnO‐W content increased. The oxygen transmission rate and water vapor transmission rate decreased from 614 to 161 cm³ m^?2 per day and 28.70 to 28.16 g m^?2 per day, respectively. However, the mechanical strength of the films decreased due to the low interfacial interaction and poor dispersion with high TZnO‐W loading. The enhanced barrier properties and good antibacterial properties of the PUA/TZnO‐W composite films indicate that these materials are potentially suitable for many packaging applications. However, further studies are needed to increase the compatibility of polymer matrix and filler. © 2012 Society of Chemical Industry     

Barrier,rheological, and antimicrobial properties of sustainable nanocomposites based on gellan gum/polyacrylamide/zinc oxide

In this study, we used a solution casting method to prepare gellan gum (G)-based ternary nanocomposite films containing polyacrylamide (P) and zinc oxide (ZnO) nanoparticles. All composites were prepared using the chemical cross-linker N,N-methylenebisacrylamide. The nanocomposites were characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction, and scanning electron microscopy. Attenuated total reflectance FTIR revealed strong hydrogen bonding interactions among gellan gum, polyacrylamide, and ZnO, which enhanced the physiochemical, thermal, and mechanical properties of the GPZnO nanocomposites. The addition of ZnO nanoparticles increased the glass transition temperature (T_g: 181.8–196.3°C), thermal stability (T_5%: 87.8–96.5°C), and char yield (23.9–29.1%) of the GP composite films, as well as their the tensile strength (from 33.5 to 43.8 MPa) and ultraviolet (UV) blocking properties (~99.2% protection against UVB [280–320 nm]). ZnO significantly influenced the rheological properties of the GP composite. The prepared GP and GPZnO nanocomposites exhibited shear thinning behavior and their viscosities decreased when there is an increase in shear rate. Storage and loss modulus increased with frequency with the addition of ZnO nanoparticles. The GPZnO films exhibited reduced hydrophilicity, moisture content, and water barrier properties compared with the GP film. The GPZnO nanocomposites exhibited effective antimicrobial activity against six different pathogens. The prepared GPZnO films could be useful in biodegradable packaging applications.     

Preparation of highly emissive,thermally stable,UV‐cured polysilsesquioxane/ZnO nanoparticle composites

A high molecular weight polysilsesquioxane (LPMSQ)/ZnO nanocomposite was prepared by blending a methacryl‐substituted polysilsesquioxane and PMMA‐coated ZnO nanoparticle (NP) followed by UV‐curing process. These LPMSQ/ZnO nanocomposites gave high thermal and mechanical stabilities originated from the rigid ladder structured siloxane backbone of LPMSQ. The polysilsesquioxane and surface‐modified ZnO nanoparticles showed excellent compatibility between MMA groups in LPMSQ‐ and PMMA‐capped ZnO nanoparticles to give well‐dispersed LPMSQ/ZnO nanocomposites. Mechanically pliant and flexible free standing films were obtained, and the photo and optical properties of these hybrid nanocomposites were examined. The high photoluminescent properties were maintained even after severe thermal treatments exceeding 400°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42333.     

Pyrene‐anchored ZnO nanoparticles through click reaction for the development of antimicrobial and fluorescent polyurethane nanocomposite

This work demonstrates the development of a multifunctional, antimicrobial and fluorescent polyurethane–ZnO hybrid nanocomposite coating with the aid of azide–alkyne click chemistry. Firstly, the surface of ZnO nanoparticles was successfully modified with 3‐azidopropyltriethoxysilane coupling agent. The azide‐terminated nanoparticles were then reacted with separately synthesized propargylpyrene in order to obtain pyrene‐anchored ZnO nanoparticles. The size of the modified nanoparticles was measured using dynamic light scattering and field emission scanning electron microscopy. Thermogravimetric analysis showed that the thermal stability of the nanoparticles decreased with surface modification. The intensities of UV absorption and fluorescence emission were improved with an increase of pyrene units on the ZnO surface. These nanoparticles were incorporated into a triazole‐rich hyperbranched polyurethane matrix in various weight percentages. It was observed that thermal stability and the intensity of UV absorption and fluorescence emission of the resulting polyurethane nanocomposite hybrid films were improved with loading of the modified nanoparticles. These hybrids are extremely resistant towards various bacterial and fungal attacks, which is attributed to the presence of the ZnO nanoparticles in the coatings. © 2014 Society of Chemical Industry     

Preparation and characterization of poly(propylene carbonate)/exfoliated graphite nanocomposite films with improved thermal stability,mechanical properties and barrier properties

Relatively high aspect ratio exfoliated graphite (EFG) particles with an average size of 7.4 µm and a nanometer sized thickness of 30–50 nm were successfully prepared by thermal treatment at 1050 °C and subsequent ultrasonication for application as a filler to improve the physical properties of eco‐friendly poly(propylene carbonate) (PPC). A series of poly(propylene carbonate)/exfoliated graphite (PPC/EFG) nanocomposite films with different EFG contents were prepared via a solution blending method. The physical properties were strongly dependent upon the chemical and morphological structures originating from the differences in EFG composition. The morphological structures, thermal properties, mechanical properties and barrier properties of the nanocomposite films were investigated as a function of the EFG content. While all of the PPC/EFG nanocomposite films exhibited good dispersion of EFG to some extent, Fourier transform infrared and SEM results revealed that solution blending did not lead to strong interactions between PPC and EFG. As a result, poor dispersion occurred in composite films with a high EFG content. By loading EFG particles, the oxygen permeabilities, moisture permeabilities and water uptake at equilibrium decreased as the EFG content increased. Compared with pure PPC, PPC/EFG nanocomposite films have enhanced molecular ordering. Specifically, the 2% PPC/EFG composite film shows greater molecular ordering than the other composite films, which results in the highest mechanical strength. In future work, the compatibility and dispersion of the PPC matrix polymer and EFG filler particles should be increased by modifying the EFG surface or introducing additives. © 2013 Society of Chemical Industry     

Mechanical properties and electrical conductivity in a carbon nanotube reinforced silicon nitride composite

The influence of carbon nanotubes (CNTs) addition on basic mechanical, thermal and electrical properties of the multiwall carbon nanotube (MWCNT) reinforced silicon nitride composites has been investigated. Silicon nitride based composites with different amounts (1 or 3 wt%) of carbon nanotubes have been prepared by hot isostatic pressing. The fracture toughness was measured by indentation fracture and indentation strength methods and the thermal shock resistance by indentation method. The hardness values decreased from 16.2 to 10.1 GPa and the fracture toughness slightly decreased by CNTs addition from 6.3 to 5.9 MPa m^1/2. The addition of 1 wt% CNTs enhanced the thermal shock resistance of the composite, however by the increased CNTs addition to 3 wt% the thermal shock resistance decreased. The electrical conductivity was significantly improved by CNTs addition (2 S/m in 3% Si₃N₄/CNT nanocomposite).     

Gelatin-clay nanocomposites of improved properties

Transparent gelatin-clay nanocomposite films were made through solution processing. These films exhibit enhanced physical performance. The Young's modulus of the composite film was 8.3 GPa, almost three times that of gelatin alone, by dispersing only 10 wt% of one type of montmorillonite clay into the nanosized phase in the gelatin. With the addition of the clay nanoparticles, the crystallinity of gelatin decreases and the melting point increases slightly. X-ray diffraction (XRD) and transmission electron microscopy (TEM) disclosed that the clay nanoplatelets are well exfoliated and dispersed, and are parallel to the plane of film in the nanocomposite film. The property enhancements of gelatin are affected by the dispersion of particles (i.e., intercalation and exfoliation), particle properties (i.e., particle aspect ratio), and particle-matrix interaction, as studied by XRD and TEM. The property enhancement can be well modeled using the Halpin-Tsai equation.     

On the interesting optical properties of highly transparent,thermally stable,spin‐coated polystyrene/zinc oxide nanocomposite films

In the present work, polystyrene/zinc oxide (PS/ZnO) nanocomposite films are prepared by simple mixing followed by film deposition, using spin‐coating technique. Although there are a few reports on the UV‐shielding properties of PS/ZnO nanocomposite films, these reports deal with rather thick films obtained by solution casting. Spin coating is a more advantageous technique where one can control the film thickness by suitably adjusting the viscosity of the solution and the spinning speed and get homogeneous films with thickness around a few hundreds of nanometers. These aspects provide the motivation for the present work where emphasis is given to investigating the optical properties of PS/ZnO nanocomposite films obtained by spin coating and analyzing the effects of each component of the composite (PS/ZnO) on the properties of the other. The nanocomposite films are found to be highly transparent throughout the visible region and the thermal stability is better compared with PS. The optical absorption of the composite films in the UV region is quite high, and this aspect highlights the prospects of applications of these films in UV shielding. The PS matrix brings about considerable surface modification of ZnO nanoparticles, resulting in the reduction of defect states within ZnO and facilitating sharp, near band edge photoluminescence emission. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of modified ZnO nanoparticle on the properties of polylactide ultrafine fibers

Zinc oxide (ZnO) was modified with hexadecyltrimethoxysilane (HDTMS) to obtain hydrophobicity and used to reinforce polylactide (PLA), an environmentally friendly polymer. The PLA/HDTMS-modified ZnO (m-ZnO) nanocomposite prepared by adding m-ZnO to the PLA matrix was fabricated into ultrafine fiber using electrospinning. Neat PLA and PLA/ZnO were used for comparisons. Structural analysis of the nanoparticles proved that the ZnO was modified successfully, and that the modification affected dispersibility and hydrophobicity, as observed by morphological, visual, and water repellency tests. The morphological analysis of the electrospun ultrafine fabrics under suitable conditions confirmed that the nanoparticles were well incorporated, and the desired functional changes were observed. Measurement of water repellency and mechanical, thermal properties were used to analyze the effect of nanoparticle modification and composition on fabrics. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47446.     

Preparation of UV-curable functionalized graphene/polyurethane acrylate nanocomposite with enhanced thermal and mechanical behaviors

Functionalized graphene nanosheets (f-GNSs) were synthesized by a simple covalent functionalization of graphene with 3-methacryloxypropyl trimethoxysilane (MPTES). The results from FTIR, XPS and XRD showed that MPTES was successfully attached onto the surface of graphene. Functionalized graphene/polyurethane acrylate (f-GNS/PUA) nanocomposites were prepared by UV radiation of PUA with f-GNS. The onset thermal degradation temperature of f-GNS/PUA nanocomposite was increased by 16 °C, at an f-GNS content of 1 wt%. Meanwhile, the storage modulus and glass transition temperature of the nanocomposites were enhanced by incorporating f-GNS into the PUA. This is believed to be attributed to that the covalent functionalization of graphene can improve both the dispersion of f-GNSs in the polymer matrix and the interfacial interactions between f-GNSs and PUA.