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.     

Physical and mechanical properties of nanocomposite barrier film containing encapsulated nanoclay

Waterborne poly(styrene‐co‐butyl acrylate) was prepared via miniemulsion polymerization in which nanoclay (Cloisite® 30B, modified natural MMT) in different concentrations was encapsulated. Scanning electron microscopy, X‐ray diffraction, and transmission electron microscopy confirmed the encapsulation and intercalated‐exfoliated structure of Cloisite® 30B within poly(styrene‐co‐butyl acrylate). The effect of nanoclay content on water vapor permeability, water uptake, oxygen permeability, thermal, and mechanical properties of thin films containing 1.5, 2.56, 3.5, and 5.3 wt % encapsulated Cloisite® 30B in poly(styrene‐co‐butyl acrylate) was investigated. The presence of encapsulated Cloisite® 30B within the polymer matrix improved tensile strength, Young's modulus, and toughness of the nanocomposites depending on the nanoclay content. Water vapor transmission rate, oxygen barrier properties, and thermal stability were also improved. The results indicated that the incorporation of Cloisite® 30B in the form of encapsulated platelets improved physicomechanical properties of the nanoclay‐polymer composite barrier films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(lactic acid)/titanium dioxide nanocomposite films: Influence of processing procedure on dispersion of titanium dioxide and photocatalytic activity

Poly(lactic acid)/titanium dioxide (TiO₂) composite films were prepared by direct melt processing using three different procedures (i.e., compression molding, twin‐screw melt extrusion, and melt extrusion and thermoforming). The effect of TiO₂ loading and processing procedures on the phase morphology and on the thermal, mechanical, and barrier properties of the obtained nanocomposites were analyzed respectively by field‐emission scanning electron microscopy‐energy dispersive spectrometry, differential scanning calorimetry, universal testing machine, and water vapor and oxygen permeability measurements. The incorporation of TiO₂ nanoparticles into the poly(lactic acid) matrix increased the crystallinity and improved the barrier properties of the composites. The maximum tensile strength was achieved at the 2% content of TiO₂ for the films produced by compression molding and twin‐screw melt extrusion, whereas the tensile strength for films produced by melt extrusion and thermoforming decreases markedly with an increasing TiO₂ content. The photocatalytic activities of the obtained nanocomposites were investigated by analyzing the degradation of methyl orange. Results confirmed that the processing procedures and the distribution of TiO₂ in the polymer matrix are the key parameters, which rule the photocatalytic behavior of composite films. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Micromorphology,mechanical, crystallization and permeability properties analysis of HA/PBAT/PLA (HA,hydroxyapatite; PBAT,poly(butylene adipate‐co‐butylene terephthalate); PLA,polylactide) degradability packaging films

In this study, the self‐made nano‐hydroxyapatite (HA) and poly(butylene adipate‐co‐butylene terephthalate) copolyesters (PBAT) were used as fillers, and composite films of HA/PLA (PLA, polylactide) and HA/PBAT/PLA systems were prepared. The micromorphology, mechanical properties, thermal properties, crystallinity, water vapor permeability and oxygen permeability of the composite films were studied. The results show that the self‐made HA has a porous rod‐like structure with a size of 30–50 nm. PBAT was dispersed uniformly in the HA/PLA matrix in the form of spherical particles and formed many pores and holes. The tensile strength, elongation at break and modulus of elasticity of HA/PLA composite films were increased by adding 10 wt% PBAT. The addition of HA and PBAT played a synergistic function in improving the crystallinity of the composite films. The water vapor and oxygen permeabilities of HA/PLA and HA/10%PBAT/PLA composite films can be regulated by adjusting the amount of HA. The results of this study indicate that composite films with higher water vapor and oxygen permeabilities exhibit great potential for applications in green packaging and fresh‐keeping packaging. © 2019 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     

Preparation and characterization of chitosan/montmorillonite‐K10 nanocomposites films for food packaging applications

Chitosan (CS)/montmorillonite‐K10 (MMTK‐10) clay composite films with different amounts of the clay MMTK‐10 (0.5, 1, 2.5, and 5%) were prepared using a solution‐casting method, and their properties were determined. The objective of this study is to prepare CS/clay nanocomposites and then to investigate the effects of clay content on mechanical, barrier, and thermal properties of these nanocomposites. The prepared films were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction analysis, transmission electron microscopy, and scanning electron microscopy. Barrier properties (oxygen and water permeability), mechanical properties (tensile strength and elongation), and thermal behaviors (thermogravimetric analysis) were investigated and compared. The water vapor and gas permeability values of the composite films decreased significantly with increasing filler concentration. Tensile strength of the composites increased significantly with the addition of clay, and elongation at break decreased with increasing clay concentration. The tensile strength of nanocomposites is up to 34.82 MPa for 5 wt% clay content, and the tensile modulus shows a 74.63% higher value than that of neat CS. The resulting films had an opaque appearance, which depended on the amount of MMTK‐10 added. The oxygen permeability decreased with the increase in MMTK‐10. The minimum oxygen permeability (1.54 cm³/m² day atm) was recorded for film with 5% MMTK‐10. The water permeability of the composite films decreased significantly between 13 and 22% when clay was added. The dispersed clay improves the thermal stability and enhances the hardness and elastic modulus of the matrix systematically with the increased loading of clay. POLYM. COMPOS., 33:1874–1882, 2012. © 2012 Society of Plastics Engineers     

Colloidal Cu nanoparticles/chitosan composite film obtained by microwave heating for food package applications

In this paper, we describe the preparation and characterization of colloidal Cu nanoparticles/chitosan composite film (composite film) by solution-casting technique with microwave heating. Effects of the incorporation of colloidal Cu nanoparticles on structure, thermal behavior, surface, barrier properties and light transmission of composite film were investigated. The antimicrobial activity of films against Staphylococcus aureus and Salmonella enterica serovar Typhimurium, were also tested. Incorporation of colloidal Cu nanoparticles on chitosan matrix improved the barrier properties of films, decreasing the oxygen permeability as well as water vapor permeability and increasing the protection against UV light. The composite film was effective in alteration of cell wall and reduction of microbial concentration in the liquid culture for both bacteria tested.     

Characteristics of soy protein isolate‐montmorillonite composite films

Soy protein isolate/montmorillonite (SPI/MMT) nanocomposite films were prepared in which MMT was used as a nanofiller at 0, 3, 6, 9, 12, and 15 wt % relative to SPI dry weight. Effects of MMT on film properties including tensile strength, elongation at break, total soluble matter, water vapor permeability, and oxygen permeability were assessed. X‐ray diffraction patterns were determined, and morphologies of SPI and the SPI‐MMT composite films were visualized by scanning electron microscopy. Mechanical and barrier properties were improved by evidenced increases in tensile strength and modulus, and decreases in permeability to water vapor and oxygen. MMT concentrations of 3%–12% were optimal for improving functional properties of the composite films. X‐ray diffraction and scanning electron microscopy examinations revealed the formation of an intercalated and exfoliated structure on the addition of MMT into the SPI matrix. We conclude that intercalated and exfoliated MMT silicates enhance mechanical and barrier properties of SPI films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of chain extrender on the compatibility,mechanical and gas barrier properties of poly(butylene adipate-co-terephthalate)/poly(propylene carbonate) bio-composites

Bio-composites consisting of poly(butylene adipate-co-terephthalate) (PBAT), poly(propylene carbonate) (PPC) and epoxy chain extender ADR 4468 were fabricated via melt blending using a torque rheometer. The relationship of the torque, melt viscosity, and molecular weight of the bio-composites was established via polymeric liquid theory to estimate the real-time chain extension reaction rate under different ADR contents. At the meantime, rheological behavior, thermal and mechanical properties, morphologies, gas barrier properties of the PBAT/PPC/ADR bio-composites were systematically characterized. The corresponding results revealed that the water vapor transmission rate (WVTR) reduced by 50% under 30 phr (parts per hundreds of resin) PPC content. The addition of ADR is beneficial to improve the mechanical properties, thermal stability and phase dispersion of PBAT/PPC without affecting the water barrier property. With 3 phr ADR, the tensile stress and elongation at break were increased from 19.5 MPa and 1184% to 26.9 MPa and 1443%, respectively. In addition, the data of the torque rheometer revealed that the chain extension reaction rate and the melt viscosity was increased with the increasing ADR content, but the reaction rate was reduced with the excessive viscosity.     

Mechanical and barrier properties of carbon nanotube reinforced PCL‐based composite films: Effect of gamma radiation

Carbon nanotube (CNT) reinforced (0.05–0.5% by wt) polycaprolactone (PCL)‐based composites were prepared by compression molding. Addition of 0.2% CNT caused a 131% improvement of tensile strength (TS) of PCL films. The tensile modulus (TM) and elongation at break (Eb) of PCL were also significantly improved with the addition of CNT. The water vapor permeability of PCL was 1.51 g·mm/m²·day but 0.2% CNT containing PCL films showed 1.08 g·mm/m²·day. Similarly, the oxygen transmission rate (OTR) of PCL films was found to decrease with the addition of CNT. But, carbon dioxide transmission rate (CO₂TR) of PCL film was improved due to incorporation of CNT. Effect of gamma radiation on PCL films and CNT reinforced PCL‐based composites were also studied. The TS of the irradiated (10 kGy) PCL films gained to 75% higher than control sample. The TS of the 0.2% CNT reinforced composite film was reached to 41 MPa at 15 kGy dose. The barrier properties of non‐irradiated and irradiated (10 kGy) PCL films and composites (0.2% CNT reinforced) were also measured. Both PCL films and composites showed lower values of WVP upon irradiation and indicated better water vapor barrier. The OTR and CO₂TR of the irradiated (10 kGy) PCL films and composites were decreased compared to their counterparts. Surface and interface morphologies of the composites were studied by scanning electron microscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

蛭石/PBAT复合薄膜的制备与性能

使用蛭石（VMT）作为填料,以可生物降解的聚对苯二甲酸-己二酸丁二醇酯（PBAT）作为基体,采用熔融-吹塑法制备出蛭石/聚对苯二甲酸-己二酸丁二醇酯（VMT/PBAT）复合薄膜,并通过添加聚苯乙烯马来酸酐共聚物（SMA）作为相容剂制备了VMT/PBAT/SMA复合薄膜。对纯PBAT薄膜、VMT/PBAT和VMT/PBAT/SMA复合薄膜的热性能、流变性能、水蒸汽阻隔性能、断面微观结构和力学性能进行了测试。结果表明,相比纯PBAT薄膜,蛭石的填充使VMT/PBAT复合薄膜的热稳定性降低,相容剂SMA的添加增强了VMT/PBAT/SMA复合薄膜的热稳定性;蛭石的添加使复合薄膜的结晶度降低了约2%。水蒸汽透过量测试表明,两种复合薄膜水蒸汽阻隔性能符合国家标准;VMT的添加使VMT/PBAT复合薄膜的拉伸强度和断裂伸长率降低,而添加相容剂SMA使VMT/PBAT/SMA复合薄膜的拉伸强度和断裂伸长率相比VMT/PBAT复合薄膜提高约10 %。     

Effect of five saturated fatty acids on the properties of sweet‐potato‐starch‐based films

To fully explore the influences of saturated fatty acids (SFAs) on the properties of sweet‐potato‐starch (SPS)‐based films, five SFAs were chosen to add to SPS. The SPS‐based films were prepared by casting. The microstructure, mechanical, optical, water vapor barrier, and thermal properties of the films were investigated. The 2.0% (w/w, on the basis of starch) SFA significantly changed the SPS pasting characteristics in the peak viscosity, breakdown, and other feature point viscosity values as determined by a Rapid Visco Analyser. The amylose molecular weights decreased as measured by high‐performance size exclusion chromatography. A thermal study with differential scanning calorimetry suggested that the addition of SFA increased the onset temperature and peak temperature. Scanning electronic microscope (SEM) images showed a continuous and uniform structure in the films with SFA. The SPS–SFA composite films showed lower light transmission and elongation at break than the control. Compared with the control films, the addition of SFA increased the tensile strength and decreased the water vapor permeability of the films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41380.     

Biodegradable high oxygen barrier membrane for chilled meat packaging

“Chilled” meat is more nutritional, healthy and hygienic than the meat kept at ambient temperature. “Poly(propylene carbonate) (PPC) and poly(vinly alcohol) (PVA) were used to prepare biodegradable three‐layer PPC/PVA/PPC films with high barrier and tensile properties. The potential benefits of the developed films were also evaluated on the shelf life of chilled meat products. Compared to PPC film, using 20 wt % PVA as an intermediate layer in PPC/PVA/PPC film remarkably enhanced oxygen barrier performance at 0 and 50 RH % by about 500 times, tensile strength by about 8 times, and Young's modulus by nine times, but no beneficial effect on water vapor barrier performance has been observed. A new “sandwich” type of completely biodegradable material with high barrier was obtained. The application of PPC/PVA20/PPC film as the packaging material of chilled meat was effectively kept the total viable count (TVC) and total volatile basic nitrogen (TVB‐N) to acceptable levels in chilled meats until 19th day of storage at 4°C, however, the spoilage occurred within 11th and 14th days of refrigerated storage in term of TVC and TVB‐N, respectively, in the chilled meats packed with only PPC. Herein, we report that PPC/PVA/PPC three‐layer film can be a promising well‐defined biodegradable material with excellent potential in chilled meat packaging. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41871.     

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     

Properties of bacterial cellulose produced in grape medium by native isolate Gluconacetobacter sp

During the production of grape wine, the occurrence of thick leathery pellicle at the air‐liquid interface was found as a contaminant. The pellicle produced was investigated with a view to use as biodegradable polymer. The bacterium that is responsible for the pellicle production was isolated, characterized and identified as Gluconacetobacter sp. Pellicle was produced in pasteurized grape extract as well as in HS medium by the isolated organism in static conditions. The purified film was subjected for Fourier transform infrared spectroscopy and C¹³ solid NMR spectroscopy analysis, which confirmed the pellicle to be a cellulosic material. Scanning Electron Micrograph showed ultra fine network structure along with cells. The films were tested for its physicomechanical characters, barrier and thermal properties. The films of 25‐μ thickness showed very high tensile strength (41.158 MPa) and elongation of 0.987 mm. The thermal properties of the films were characterized by Differential scanning calorimetry and Thermo gravimetric analysis. The melt peak temperature was found to be 111.65°C. The percentage of weight loss was found to be 20% at 327.86°C. Barrier properties (oxygen transmission rate and water vapor transmission rate), indicated a high oxygen barrier but low water barrier. This is the first report on the barrier properties of bacterial cellulose from Gluconacetobacter sp. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of SiO2/EVA on the mechanical properties,permeability, and residual solvent of polypropylene packaging films

The surface of nano‐silica was modified by ethylene/vinyl acetate (EVA) emulsion and then blended with polypropylene (PP) to yield a nano‐silica/PP composite material. This composite was intended to enhance the mechanical properties of PP, improve its melting point and degree of crystallinity, reduce its oxygen permeability and water vapor permeability, decrease the adsorption of PP packaging films against organic solvents, and improve the films' performance for food safety. The experiments showed that the crystallinity of PP modified by nano‐silica increased, leading to enhanced mechanical and barrier properties, while its melting point rose. Meanwhile, the residual solvent value of the modified PP films was reduced by 10–90%. POLYM. COMPOS., 101–107, 2016. © 2014 Society of Plastics Engineers     

Enhancing the mechanical and barrier properties of chitosan/graphene oxide composite films using trisodium citrate and sodium tripolyphosphate crosslinkers

This study investigated the effect of ionic crosslinking on the mechanical, barrier, and optical properties of chitosan (CS) and CS/graphene oxide (CSGO) composite films using trisodium citrate (CIT) and sodium tripolyphosphate (TPP) solutions of different concentrations (0.5, 1.0. 2.0, and 3.0% w/v). Successful crosslinking was confirmed by Fourier-transform infrared spectroscopy. The hydrophilicity and light transmittance decreased significantly (p < 0.05) with the increase in concentration of both crosslinking agents. The CS films crosslinked with 3.0% w/v TPP exhibited significant (p < 0.05) improvements in barrier properties, achieving a 51% decrease of water vapor permeability and 59% decrease in oxygen permeability, in comparison to neat CS film. In addition, TPP-crosslinked CSGO films experienced an 82% and 42% improvement in tensile strength and elongation at break, respectively. Overall, crosslinked CS and CSGO films possess significantly improved properties and have great potential to be further studied as food packaging materials.     

Effect of morphology on the permeability,mechanical and thermal properties of polypropylene/SiO2 nanocomposites

Spherical silica nanoparticles with 20 and 100 nm diameters and organic‐template layered silica nanoparticles synthesized by the sol‐gel method were melt blended with a polypropylene (PP) matrix in order to study and quantify their effect on the oxygen and water vapor permeability and mechanical and thermal behavior. With regard to barrier properties, the spherical nanoparticles barely increased the oxygen permeability at low loads (≤10 wt%); meanwhile the layered nanoparticles dramatically increased it even at low loading (<5 wt%) probably due to the percolation effect. The changes in water vapor permeability were similar to those in oxygen permeability. The repulsive interaction between nanoparticles and PP forms interconnecting voids where the gas permeates. Tensile stress–strain tests showed that the composites present up to a 56% increase in the elastic modulus with spherical nanoparticles at 20 wt%, while layered nanoparticles show a decrease probably due to agglomerations and voids. Thermogravimetric analysis under inert conditions showed that the nanoparticles improved the PP thermal degradation process through the adsorption of volatile compounds on their surface, where the smaller spherical nanoparticles show the greatest stabilization. © 2015 Society of Chemical Industry     

Development of isotactic polypropylene and stearic acid-modified calcium carbonate composite: a promising material for microwavable packaging

Isotactic polypropylene (PP) composite films were developed, with incorporation of CaCO₃ particles as active filler. Stearic acid was used for the surface treatment of CaCO₃ to provide composite films having improved mechanical, thermal and barrier properties against oxygen as well as water vapor, in comparison to neat PP films. The filler was melt mixed with PP in a twin-screw extruder, and the films produced through melt blowing. A slight reduction in T _g values of the filled PP films was observed, along with an increase in the overall crystallization extent relative to neat PP films. X-ray diffraction data confirmed that the CaCO₃ particles served as a β-nucleating agent capable of promoting the formation of the β-crystalline phase of PP and reducing the spherulite size, with stearic acid-coated CaCO₃ being most effective in promoting these features. Exposing the films to microwave radiation altered their properties; at low irradiation power, the T _g values and the degree of β-crystallization were enhanced, and barrier properties against oxygen and water vapor showed improvements. In contrast, no significant changes in the appearance of the film surface were evident highlighting the potential of these PP-based composite films in microwave packaging applications.     

Morphologies and properties of nanocomposite films based on a biodegradable poly(ester)urethane elastomer

Biodegradable poly(ester)urethane (PU) elastomer‐based nanocomposite films incorporated with organically modified nanoclay were prepared with melt‐extrusion compounding followed by a casting film process. These films were intended for application as biodegradable food packaging films, with their enhanced gas barrier, mechanical, and thermal properties and good flexibility. From both X‐ray diffraction measurements and transmission electron microscopy observations, the coexistence of intercalated tactoids and exfoliated silicate layers in the compounded PU/clay nanocomposite films was confirmed. In addition, the morphology exhibited a clay dispersion state in the matrix and was influenced by the incorporated nanoclay content. The effects of the nanoclay loading level on the thermal, mechanical, and barrier properties of the compounded nanocomposites were also investigated. As a result, it was revealed that the addition of nanoclay up to a certain level resulted in a remarkable improvement in the thermal properties in terms of thermal stability and the degree of thermal shrinkage; mechanical properties, including dynamic storage modulus and tensile modulus; and oxygen/water‐vapor barrier properties of the nanocomposite films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011