Effect of compatibilization on the oxygen‐barrier properties of poly(ethylene terephthalate)/poly(m‐xylylene adipamide) blends

The improvement of the oxygen‐barrier properties of poly(ethylene terephthalate) (PET) via blending with an aromatic polyamide [poly(m‐xylylene adipamide) (MXD6)] was studied. The compatibilization of the blends was attempted through the incorporation of small amounts of sodium 5‐sulfoisophthalate (SIPE) into the PET matrix. The possibility of a transamidation reaction between PET and MXD6 was eliminated by ¹³C‐NMR analysis of melt blends with 20 wt % MXD6. An examination of the blend morphology by atomic force microscopy revealed that SIPE effectively compatibilized the blends by reducing the MXD6 particle size. Thermal analysis showed that MXD6 had a nucleating effect on the crystallization of PET, whereas the crystallization of MXD6 was inhibited, especially in compatibilized blends. Blending 10 wt % MXD6 with PET had only a small effect on the oxygen permeability of the unoriented blend when it was measured at 43% relative humidity, as predicted by the Maxwell model. However, biaxially oriented films with 10 wt % MXD6 had significantly reduced oxygen permeability in comparison with PET. The permeability at 43% relative humidity was reduced by a factor of 3 in compatibilized blends. Biaxial orientation transformed spherical MXD6 domains into platelets oriented in the plane of the film. An enhanced barrier arose from the increased tortuosity of the diffusion pathway due to the high aspect ratio of MXD6 platelets. The aspect ratio was calculated from the macroscopic draw ratio and confirmed by atomic force microscopy. The reduction in permeability was satisfactorily described by the Nielsen model. The decrease in the oxygen permeability of biaxially oriented films was also achieved in bottle walls blown from blends of PET with MXD6. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1361–1370, 2005     

Charge storage behavior of isotropic and biaxially‐oriented polypropylene films containing α‐ and β‐nucleating agents

A study on the influence of the crystal modification (α and β) of isotactic polypropylene (i‐PP) films on the resulting electret properties is presented. Two commercial nucleating agents, sodium 2,2′‐methylene‐bis(4,6‐di‐tert‐butylphenyl)‐phosphate (NA11) and N,N′‐dicyclo‐hexyl‐2,6‐naphthalene‐dicarbox‐amide (NU100), were employed in this investigation. Isothermal charge decay was measured at 90°C. In hot pressed isotropic polypropylene films, no significant differences in the charge storage properties were observed for α‐ and β‐nucleated specimens. In addition, the article presents the influence of the nucleating agents at different concentrations on the PP‐film morphology of biaxially stretched films with respect to electret features. It was possible to prepare elongated cavities with the virtually insoluble NA11 additive during stretching, even at concentrations below 0.3 wt %. These films displayed slightly improved electret properties in comparison to stretched neat PP films due to generated cavities acting as barriers for the drift of charges. Various draw ratios were also studied for i‐PP films with 0.15 wt % NA11. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 650–658, 2006     

Poly(ethylene terephthalate)/poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate)/clay nanocomposites: Effects of biaxial stretching

In this study, we fabricated poly(ethylene terephthalate) (PET)/clay, PET/poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate) (PETG), and PET/PETG/clay nanocomposite plates and biaxially stretched them into films by using a biaxial film stretching machine. The tensile properties, cold crystallization behavior, optical properties, and gas and water vapor barrier properties of the resulting films were estimated. The biaxial stretching process improved the dispersion of clay platelets in both the PETG and PET/PETG matrices, increased the aspect ratio of the platelets, and made the platelets more oriented. Thus, the tensile, optical, and gas‐barrier properties of the composite films were greatly enhanced. Moreover, strain‐induced crystallization occurred in the PET/PETG blend and in the amorphous PETG matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42207.     

Effect of uniaxial stretching on thermal,oxygen barrier,and mechanical properties of polyamide 6 and poly(m‐xylene adipamide) nanocomposite films

In this study, the effect of uniaxial stretching on the thermal, oxygen barrier and mechanical properties of aliphatic polyamide 6 (PA6) and aromatic Poly(m‐xylene adipamide) (MXD6) nylon films as well as their in‐situ polymerized nanocomposites with 4 wt% clay were studied. Cast films were prepared by extrusion process and rapidly cooled using an air knife. The precursor films were uniaxially stretched at 110°C with draw ratios varying from 1.5 to 5. DSC results showed that the cold crystallization temperature (T_cc) of the uniaxially stretched MXD6 and MXD6/clay films drastically shifted to the lower temperatures when draw ratio increased. The aromatic nylon films had lower oxygen permeability than those of the aliphatic films, due to more rigidity and chain packing. However, the oxygen permeability of the stretched films increased with draw ratio (DR) up to a critical value for each sample, while further stretching resulted in a reduction in the oxygen permeation. This phenomenon was related to the changes in free volume upon uniaxial stretching. The ability of different geometrical models to describe the experimental relative permeability data was investigated. The Bharadwaj model that took into account clay orientation was the most successful one to predict the oxygen barrier characteristics of the stretched nanocomposites at high draw ratios. The Young's modulus and tensile strength of the aliphatic and aromatic nylons increased with uniaxial deformation, while the flexibility and elongation at break of the former decreased with increasing DR. A larger increase in the Young's modulus of the uniaxially stretched nanocomposite films compared with the neat samples was observed and could be related to the improvement in the clay orientation as well as a better alignment of the crystalline phase due to incorporating the clay platelets in the polymer matrix. In contrast, the flexibility of the stretched MXD6 improved remarkably (ca., 25 times) compared with the precursor film (DR = 1) when the draw ratio increased to 1.5. This could be related to the effect of hot stretching on the enhancement of polymer chains relaxation and mobility at low draw ratios. POLYM. ENG. SCI., 55:1113–1127, 2015. © 2014 Society of Plastics Engineers     

Packaging‐related properties of alkyd‐coated,wax‐coated,and buffered chitosan and whey protein films

Packaging‐related properties of coated films of chitosan–acetic acid salt and whey protein concentrate (WPC) were studied. Chitosan (84.7% degree of deacetylation) and WPC (65–67% protein) were solution cast to films. These films are potential oxygen barriers for use in packaging. Coatings of wax or alkyds were used to enhance the water‐barrier properties. The packaging‐related properties of chitosan films treated in a buffering solution, with a pH of 7.8, were also investigated. The coated films were characterized with respect to Cobb absorbency, overall migration to water, water vapor transmission rate, and oxygen permeability. The creasability and bending toughness were determined. The wax was a more efficient barrier to liquid water and 90–95% relative humidity than the alkyd. However, the alkyd‐coated material had superior packaging‐converting properties. The alkyd‐coated WPC and chitosan–salt films were readily folded through 180° without any visible cracks or delamination. The overall migration from the alkyd‐coated materials was below the safety limit, provided the coat weight was higher than 7.5 mg/cm² on WPC and 2.1 mg/cm² on chitosan–salt. The barrier properties of chitosan film under moist conditions were improved by the buffer treatment. However, the buffering also resulted in shrinkage of the film. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 60–67, 2004     

Structure and properties of melt‐stretching polypropylene/silicon dioxide compound microporous membrane

To improve the strength and modulus of polypropylene (PP) microporous membrane, the nano‐silicon dioxide (SiO₂) was introduced and the influence of SiO₂ content on the structure and properties of initial precursor film and stretched microporous membrane was investigated. It was found that with increasing SiO₂ content to 2%, the crystalline orientation degree of precursor film was decreased from 0.41 to 0.32, but the elastic recovery value did not change much. The mean pore diameter of the stretched microporous membrane was increased from 28.3 to 32.5 nm. The Gurley value (characterizing the air permeability) only decreased from 200 to 194 s. The tensile strength and elastic modulus were increased by 33.3 and 72.0 MPa, respectively. But when the SiO₂ content was 10%, the air permeability of stretched microporous membrane was apparently decreased by 21.5%. Compared with that of microporous membrane without SiO₂, the tensile strength was increased by only 1.6 MPa. It was concluded that the introduction of 2% content of SiO₂ resulted in the improvement of mechanical properties, at the same time did not deteriorate the pore structure and properties of PP microporous membrane. POLYM. COMPOS., 37:2684–2691, 2016. © 2015 Society of Plastics Engineers     

Morphology–property relationship in oriented PET films: Microstructural reorganization during heat treatment

Morphology–property relationships for simultaneously biaxially stretched films and heatset with fixed dimensions in the temperature range of 100–240°C have been studied. The observed transition in various properties at 180°C can be explained on the basis of microstructural changes caused by competition among several processes, such as crystallization, solid-state thickening, melting, and molecular relaxation as well as by melting and recrystallization. The resulting structures and, thereby, the properties are different in temperature Regime-II (T_g to T_max) and Regime-III (T_max to T_m). In Regime-II, the high rate of crystallization compared to the rate of molecular relaxation develops a constrained amorphous phase, whereas the predominant melting and recrystallization process in Regime-III generates the relaxed amorphous phase. The structural reorganization during heat treatment is almost the same for uniaxially oriented film, fibers, and biaxially oriented films prepared under similar processing conditions. © 1994 John Wiley & Sons, Inc.     

Morphology and texture development of uniaxially stretched poly(ethylene naphthalene‐2,6‐dicarboxylate)

The texture development of PEN films with different semicrystalline morphologies have been studied by X‐ray diffraction. These different structures have been obtained by uniaxially stretching PEN amorphous films at 100 and 160°C (below and above T_g) at different drawing ratios. Samples have also been characterized by DSC to determine the crystallinity ratios, the crystallization, and melting temperatures. To define the orientation of crystallites in the oriented samples, pole figures have been constructed, as a function of temperature and drawing ratio (DR) in the range 1.5–4. In the range from DR = 2 to 4 the orientation is clearly uniplanar‐axial. At T_draw = 100°C the crystallinity shown by DSC analysis is higher than the sample stretched at 160°C. The orientation is also higher when samples are stretched at 100°C. The naphthalene rings mainly stay in the plane of the film with a lower fraction perpendicular to the plane of the film. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 395–401, 2007     

Development of transdermal drug‐delivery films with castor‐oil‐based polyurethanes

Two different types of polyurethanes (PUs) were prepared with castor oil, ethylene glycol, isophorene diisocyanate and castor oil, and isophoren diisocyanate and poly‐(ethylene glycol) (400 or 600). PU films were prepared and characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, and gel permeation chromatography. We prepared transdermal patches by loading different amounts of drug, plasticizer, and penetration enhancer. In vitro drug permeability through the castor‐oil‐based aliphatic PU patches was examined with a Keshary–Chien diffusion cell. The effect of castor oil on the film‐forming properties and the effect of penetration enhancers on diffusion characteristics of indomethacin (IDM) drug through the castor‐oil‐based PU were investigated. Prolonged release of IDM was observed from the prepared PU patches. In vitro drug diffusion revealed that slow and prolonged release of IDM was achieved in the absence of penetration enhancers. The use of penetration enhancers showed a significant effect on drug diffusion. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 779–788, 2007     

Effect of solvent on properties of solution‐cast dense SPPO films

The effect of solvent on properties of solution‐cast dense films was investigated using high molecular weight sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO) and five different solvents having relatively similar molar volumes. The study revealed that polymer–solvent interactions existing in casting solution primarily determine the concentration of residual solvent and surface morphology of the films. On the other hand, the O₂ and CO₂ permeabilities, which for most permeable films were more than three times greater than for the least permeable ones, appear to be governed by the volatility of solvent in casting solution. At the same time, the more permeable films showed lower O₂/N₂ and CO₂/CH₄ permeability ratios than the less permeable ones. In addition to physical factors such as polymer–solvent interactions and volatility of solvent in casting solution, the differences in gas transport properties of SPPO films could arise from the formation of quaternary salts—in particular, in the case of films prepared from the pyridine solution. The analysis of casting solution properties, surface images by atomic force microscopy, and gas transport properties allowed us to associate defective structures of some SPPO films with a specific surface morphology and a particular combination of solvent properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1100–1110, 2003     

Gas barrier and wetting properties of whey protein isolate‐based emulsion films

The aim of this research was to investigate the effect of rapeseed oil concentration (1–3% w/w) on the water vapor, oxygen and carbon dioxide permeability, water vapor sorption and surface properties of whey protein isolate emulsion‐based films. The water contact angle as affected by oil content, film side and time was analyzed. The effect of temperature (5 and 25°C) on the water vapor permeability (WVP), water vapor sorption kinetics and diffusion coefficient was also studied. The results showed that the incorporation of a lipid phase to whey protein film‐forming solutions was able to decrease the WVP, water hydrophilicity (increasing water contact angle) and water transfer of whey protein films. However, the films containing oil were more permeable to oxygen and carbon dioxide. Significantly higher values of WVP and diffusion coefficient were obtained at 5°C than at 25°C, indicating that storage temperature should be taken into account when designing the composition of edible films and coatings for food applications. POLYM. ENG. SCI., 59:E375–E383, 2019. © 2018 Society of Plastics Engineers     

Construction of a choline biosensor through enzyme immobilization on a poly(2‐hydroxyethyl methacrylate)‐grafted Teflon film

An amperometric choline biosensor was constructed by immobilizing choline oxidase (ChO) on poly(2‐hydroxyethyl methacrylate) (PHEMA)‐grafted Teflon (polytetrafluoroethylene, PTFE) film. Grafting was achieved by γ irradiation. PHEMA‐grafted Teflon films were activated with epichlorohydrin or glutaraldehyde to achieve covalent immobilization of enzyme onto the film. To decrease the diffusional barrier caused by the enzyme‐immobilized film, the film was stretched directly on the electrode. The PHEMA‐grafted Teflon film, therefore, had to have appropriate mechanical properties. Glucose oxidase (GOD) was used in the determination of optimum immobilization conditions, then these were applied to ChO. With GOD, the effect of activation type and film position in electrode on enzyme activity was studied and the highest catalytic activity was obtained when the enzyme was immobilized using glutaraldehyde and the film was stretched over the electrode surface. Further studies revealed that the films activated with glutaraldehyde, immobilized in 2 mg/mL ChO concentration, and stretched directly on the electrode were suitable (specific activity, 0.427 ± 0.068 U mg^?1) for use in the choline biosensor. The linear working range of this biosensor was found to be 52–348 μM, with a 40 ± 5 μM minimum detection limit. The response of the sensor, however, decreased linearly upon repeated use. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Influence of magnesium sulfate whiskers on the structure and properties of melt‐stretching polypropylene microporous membranes

The influence of magnesium sulfate (MgSO₄) whiskers on the structure and properties of polypropylene cast films and stretched microporous membranes was investigated. We found that for the cast films, MgSO₄ showed some nucleation effects, and the introduction of MgSO₄ led to the decrease of the orientation degree along the machine direction (MD), whereas that along the transverse direction (TD) was improved; this indicated that MgSO₄ whiskers were mainly arranged along the TD. The introduction of MgSO₄ up to 10 wt % did not induce apparent changes in the pore structure and air permeability properties of the stretched microporous membranes but improved the electrolyte absorption ability. The most pronounced change for the stretched microporous membranes was the strength along the TD. It was increased by 110% when the MgSO₄ content was 2 wt %. During the fabrication of microporous membranes, only stretching along the MD was carried out to initiate pore formation; this resulted in a lower strength along the TD. This study gave us a method for improving the mechanical properties of stretched microporous membranes along the TD. The obtained microporous membranes with better electrolyte absorption and higher mechanical strength along the TD could be used in lithium‐ion batteries as separators. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43884.     

Gas transport and thermal characterization of mono‐ and di‐polyethylene films used for food packaging

The permeability of carbon dioxide, oxygen, nitrogen, and air through commercial monolayer and multilayer films, based on polyethylene (PE), biaxially oriented polypropylene (BOPP), and polyamide (PA), used for food packaging is reported. The influence of temperature (from 10 to 60°C) on permeability and DSC characteristics changes was also analyzed. Literature data for gas permeability of the mentioned monofilms are quite variable due to differences in additives, thermal history, and crystallinity. In this work, the highest gas permeability is obtained for PE film at the higher temperature (50–60°C). Laminates exhibit different gas permeation behavior from that of monofilms. Generally, gas solubility coefficient increases at higher temperature (with an exception of PA/PE and BOPPcoex.met/PE), being higher for monofilms in comparison with laminates, while diffusion coefficients are lower for monofilms in comparison with laminates. The temperature dependence of the permeability, diffusivity, and solubility of gases shows two different regions in PE, BOPPcoex/PE (10–40°C and 40–60°C), PA/PE, and BOPPcoex.met (10–30°C and 40–60°C) films. Correlation between activation energies for permeation and diffusion as well as heat of sorption and 17 gas properties is performed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1590–1599, 2006     

Texture and morphology of biaxially stretched poly(ethylene naphthalene‐2,6‐dicarboxylate)

The orientation of poly(ethylene naphthalene‐2,6‐dicarboxylate) (PEN) films with different morphologies were studied by wide‐angle X‐ray diffraction. Different structures were obtained by thermally treating biaxially stretched PEN samples. Virgin and thermally treated (1 h at 240, 250, and 260°C) samples of PEN bioriented films were characterized by DSC to determine the glass‐transition temperature and the crystallinity ratio. To define the orientation of crystallites in the 25 μm thick bioriented samples, pole figures were recorded for various PEN samples, as a function of their position in the transverse drawing direction. The significant result is that there is a dominant crystal population, whose c‐axis direction varies from +45° at one sample edge to ?45° at the other edge, the orientation at the center being parallel to the transverse direction. There is also a secondary population, which can be seen only near the center. DSC studies also showed that by increasing the annealing temperature the crystallinity ratio was increased and pole figures showed that the texture was modified, probably because of disorientation mainly from an annealing temperature of 260°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2224–2232, 2003     

Microporous polypropylene films containing ultrafine silica particles

Sol–gel reaction of tetraethoxysilane was carried out in molten polypropylene with the aid of an extruder. The resultant composites were used to mold sheets containing finely dispersed SiO₂ particles. These sheets were biaxially stretched to prepare microporous films, of which some properties were estimated (pore size, porosity, specific surface area, and gas permeability). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1489–1494, 1999     

Mechanical and barrier properties of edible starch–protein‐based films

The present investigation dealt with the mechanical properties, water‐vapor transmission behavior at different relative humidity conditions, and DSC thermograms of edible films formulated using various proteins (casein, gelatin, albumin) in combination with starch and nonthermal as well as intense thermal blending. Nonthermal blended film showed in the DSC thermogram a double T_g, indicating poor miscibility of the components and, hence, a poor film‐forming property. However, the DSC thermogram of all the films based on intense thermal blending showed a single T_g, indicating the complete molecular miscibility of the components. Casein‐based film showed a lower water‐vapor transmission rate, water gain at different relative humidity conditions, and higher tensile strength compared to its counterparts containing gelatin and albumin. Since the casein–starch blend gave better film properties, a blend of hydrophobic carnauba wax and casein was prepared to compare the properties of hydrophilic–hydrophilic and hydrophobic–hydrophilic blends. Both these blends compared well with respect to the water‐vapor transmission rate. Wax‐based film showed multiphased behavior in the DSC thermograms and the percent elongation was lower as compared to the casein–starch blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 64–71, 2003     

Control of well‐defined crater structures on the surface of biaxially oriented polypropylene film by adding nucleators

While it is common to add anti‐blocking agents to biaxially oriented polypropylene (BOPP) films for general use in order to prevent blocking against each other, the technology of crater‐like film surface roughness formed on the BOPP films without any additives is well known in the industrial BOPP film areas. Numerous studies have been reported on the crater‐like film surface roughness on the BOPP films since the 1980s, but its formation mechanism and the controlling method of the crater‐like film surface roughness are yet to be clarified. In our previous reports, we presented a new hypothesis of crater formation mechanism from a new point of view on sheet morphology and crater shape on the BOPP film surface. It was strongly influenced by the crystal grain shape in the surface layer of PP sheet. In this report, it was clarified that a nucleator has a big influence on the formation of the crystal grains in the surface layer of PP sheets and on the formation of craters. In addition, craters did not form on the BOPP films stretched from the sheet of which the skin layer with crystal grain was shaved, even though β crystal still remained. It was clarified that the crystal grain is trans‐crystal from the observation using TEM. Therefore, it is concluded that the existence of β crystals in the surface layer of PP sheets is not essential in order to produce craters on BOPP films, but trans‐crystals are necessary to form the craters. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3555–3564, 2013     

Preparation of siloxane–silsesquioxane hybrid thin films for large‐scale‐integration interlayer dielectrics with excellent mechanical properties and low dielectric constants

Several kinds of homogeneous organic–inorganic hybrid polymer thin films were designed with improved mechanical properties and low dielectric constants (<3.0). Novel soluble siloxane–silsesquioxane hybrid polymers were synthesized with cyclic and/or cage silane monomers, which had triorganosiloxy (R₃Si_1/2), diorganosiloxane (R₂SiO_2/2), and organosilsesquioxane (RSiO_3/2) moieties with ethylene bridges at the molecular level, by the hydrolysis and condensation of 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane (a cyclic monomer). The electrical properties of these films, including the dielectric constant (～2.51), leakage current (6.4 × 10^?11 A/cm² at 0.5 MV/cm), and breakdown voltage (～5.4 MV/cm) were fairly good. Moreover, the mechanical properties of the hybrid films, including the hardness (～7 GPa), modulus (～1.2 GPa), and crack‐free thickness (<2 μm), were excellent in comparison with those of previous spin‐on‐glass materials with low dielectric constants. The excellent mechanical properties were proposed to be due to the high contents of Si? OH groups (>30%) and the existence of ethylene bridge and siloxane moieties in the hybrid polymer precursors. In addition, the mechanical properties of the hybrid films were affected by the contents of the cagelike structures. The more cagelike structures a hybrid film contained, the worse its mechanical properties were. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 626–634, 2003     

Gas permeability of thin dense films from polymer blend of thermoplastic elastomer and polyolefin

Stretched thin films composed of a thermoplastic elastomer, a polystyrene‐block‐poly(ethylene butylene)‐block‐polystyrene triblock copolymer (SEBS), and polyolefins, poly(ethylene‐co‐ethylacrylate) and poly(ethylene‐co‐propylene), were obtained by blow‐molding, uniaxial stretching, and cooling to room temperature and the gas permeability of the stretched films was investigated. When the as‐blown annealed film was subjected to uniaxial stretching in the machine direction, P_O2 and P_N2 increased with an increase in the stretching ratio K and approached a constant value at high stretching ratios. In addition, P_O2/P_N2 decreased gradually with K and approached a value of 2.95–3.0. The reason for this unique gas permeation behavior is that the molecular mobility of poly(ethylene butylene) chains in a direction normal to the film increases and reaches an equilibrium state at around K = 4.5. The change in gas permeability of the stretched films can be explained using a deformation model for the SEBS matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39386.