Preparation of oxygen gas barrier poly(ethylene terephthalate) films by deposition of silicon oxide films plasma‐polymerized from a mixture of tetramethoxysilane and oxygen

To prepare silicon oxide (SiOx)‐deposited poly(ethylene terephthalate) films with high oxygen gas barrier capability, SiOx deposition by plasma polymerization has been investigated from the viewpoint of chemical composition. Tetramethoxysilane (TMOS) is suitable as a starting material for the synthesis of the SiOx films. The SiOx deposition under self‐bias, where the etching action occurs around an electrode surface, is effective in eliminating carbonaceous compounds from the deposited SiOx films. There is no difference in the chemical composition between the SiOx films deposited under self‐bias and under no self‐bias. The SiOx films are composed of a main component of Si O Si networks and a minor component of carbonized carbons. The SiOx films deposited under no self‐bias from the TMOS/O₂ mixture show good oxygen gas barrier capability, but the SiOx films deposited under the self‐bias show poor capability. The minimum oxygen permeation rate for poly(ethylene terephthalate) films deposited SiOx film is 0.10 cm³ m⁻² day⁻¹ atm⁻¹, which corresponds to an oxygen permeability coefficient of 1.4 × 10⁻¹⁷ cm³‐cm cm⁻² s⁻¹ cm⁻¹ Hg for the SiOx film itself. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2091–2100, 1999     

Improving oxygen barrier properties of poly(ethylene terephthalate) by incorporating isophthalate. II. Effect of crystallization

The present study examined crystallization of poly(ethylene terephthalate) (PET) and a series of random and blocky copolymers in which up to 30% of the terephthalate was replaced with isophthalate. Isothermal crystallization kinetics and direct observation of the spherulitic morphology revealed that the blocky copolymers crystallized more rapidly than PET, at least in part, as the result of enhanced spherulite nucleation. The statistical copolymers with 10 and 20% isophthalate achieved almost the same level of crystallinity as that of the blocky copolymers. The statistical copolymers with 10% isophthalate crystallized almost as fast as PET, although the statistical copolymer with 20% isophthalate crystallized much more slowly. Crystallization substantially reduced the oxygen permeability. Analysis of oxygen‐transport parameters in terms of a two‐phase structural model that considered a dispersion of lower‐permeability spherulites in an amorphous matrix of higher permeability revealed that dedensification of the PET interlamellar amorphous regions was responsible for the unexpectedly high oxygen solubility of crystallized PET. In contrast, copolymerization with isophthalate prevented dedensification of the interlamellar amorphous regions. As a result, crystallization was more effective in reducing the oxygen permeability. It was speculated that segregation of kinked isophthalate units to the amorphous regions of the spherulite relieved constraint on the interlamellar amorphous chain segments. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1629–1642, 2005     

Improving oxygen barrier properties of poly(ethylene terephthalate) by incorporating isophthalate. I. Effect of orientation

The present study examined poly(ethylene terephthalate) (PET) and a series of statistical and blocky copolymers in which up to 30% of the terephthalate was replaced with isophthalate by copolymerization and melt blending, respectively. Some level of transesterification during processing of melt blends resulted in blocky copolymers, as confirmed by NMR. Random and blocky copolymers exhibited similar properties in the glassy state, including a single glass transition, due to miscibility of the blocks. However, random copolymerization effectively retarded cold‐crystallization from the glass whereas blocky copolymers readily cold‐crystallized to a crystallinity level close to that of PET. The polymers were oriented at four temperatures in the vicinity of the T_g and characterized by oxygen transport, wide‐angle X‐ray diffraction, positron annihilation lifetime spectroscopy, and infrared spectroscopy. Orientation of all the copolymers resulted in property changes consistent with strain‐induced crystallization. However, blocky copolymers oriented more easily than random copolymers of the same composition and after orientation exhibited slightly lower oxygen permeability, higher density, and higher fraction trans conformers. Analysis of oxygen solubility based on free volume concepts led to a two‐phase model from which the amount of crystallinity and the amorphous phase density were extracted. Dedensification of the amorphous phase correlated with the draw temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1615–1628, 2005     

Effect of morphology on barrier properties of poly(ethylene terephthalate)

The effects of morphology on the barrier properties of poly(ethylene terephthalate) (PET) have been investigated. Various levels of crystallinity can be developed in PET as a result of thermal exposure, orientation, and heat setting. The morphologies of the crystalline phase are affected by the conditions of their formation. As a result of morphological differences, samples with equivalent levels of crystallinity have been found to exhibit different oxygen barrier properties. These differences are most apparent at low and intermediate levels of crystallinity. For thermally crystallized systems, at the same crystalline content, increasing superstructure size in the crystalline phase leads to greater tortuosity for the permeant molecules, resulting in lower permeability. For stretched and heat set PET, transport properties can be correlated with birefringence as well as overall orientation, measured in terms of fraction of molecules in the trans or extended chain conformation. At high levels of crystallinity, where the spherulites become volume filling, permeation takes place primarily through the interlamellar regions of the crystalline phase and is controlled by level of crystallinity, independent of the mode of crystallization. The barrier properties of PET, before spherulitic impingement occurs, are governed by the size and number of spherulites as well as by the amorphous orientation present in non‐crystalline regions. POLYM. ENG. SCI., 45:400–409, 2005. © 2005 Society of Plastics Engineers     

Porous poly(L‐lactic acid)/poly(ethylene glycol) blend films

Poly(L ‐lactic acid) (PLLA: M_w = 19.4 × 10⁴)/poly(ethylene glycol) (PEG: M_w = 400) blend films were formed by use of a solvent‐cast technique. The properties and structures of these blend films were investigated. The Young's modulus of the PLLA decreased from 1220 to 417 MPa with the addition of PEG 5 wt %, but the elongation at break increased from 19 to 126%. The melting point of PLLA linearly decreased with increases in the PEG content (i.e., pure PLLA: 172.5°C, PLLA/PEG = 60/40 wt %: 159.6°C). The PEG 20 wt % blend film had a porous structure. The pore diameter was 3–5 μm. The alkali hydrolysis rate of this blend film was accelerated due to its porous structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 965–970, 2004     

UV curable coatings for improved gas barrier properties of poly(ethylene terephthalate)

A new high-barrier coating based on methyl (α-hydroxymethyl)acrylate (MHMA) for poly(ethylene terephthalate) (PET) was developed along with the process for preform dipping and cure prior to blow molding into bottles. The UV curable coating gives excellent gas barrier improvement when coated onto PET biaxially oriented thin films. Blown bottle side walls from coated PET preforms also show 2–3 times improvement over uncoated side walls. The effect of photoinitiator concentration, initiator types, and temperature on photopolymerization kinetics of MHMA was investigated. Once the photoinitiator, Irgacure 819^®, concentration became larger than 1 mol%, a decrease in rate of propagation was observed. The conversion also decreased with higher initiator concentration. Irgacure 819^® reduced the auto-acceleration peak and reached maximum rates of polymerization much faster than Irgacure 651^®. It also gave a slightly higher conversion. Overall conversion for combinations of these photoinitiators was high, above 80%. Real-time FTIR (RT-FTIR) studies of copolymerization of MHMA and methyl methacrylate (MMA) showed that conversion was fairly high up to 25 mol% MMA. However, once MMA feed ratio exceeded 10 mol%, a decrease in barrier performance was observed.     

Effect of recycling on the properties of poly(ethylene terephthalate) films

Different proportions of recycled poly(ethylene terephthalate) (PET) films were blended with virgin PET and evaluated for physicomechanical, chemical, thermal, optical and barrier properties. The safety evaluation of the films for food contact applications has also been carried out. The variations in properties, such as tensile behaviour, impact strength, tear resistance, burst strength, gloss, haze, barrier properties, crystallization temperature and melting temperature, are reported. © 2000 Society of Chemical Industry     

Antiplasticization-based enhancement of poly(ethylene terephthalate) barrier properties

Incorporation of selected low molecular weight diluents (LMWDs) into poly(ethylene terephthalate) (PET) significantly improves oxygen and carbon dioxide barrier properties. A so-called Barrier Improvement Factor (BIF), defined as the ratio of permeability of pure polymer to that of antiplasticized polymer, provides a useful indication of improved barrier properties. The average BIF was found to be 1.20 (±0.02) and 1.34 (±0.03) for O₂ and 1.25 (±0.01) and 1.41 (±0.01) for CO₂ in PET containing - 2.32% phenacetin, or 1.95% acetanilide, respectively. The reduced permeability coefficient in each PET sample is attributed to antiplasticization, and justified by the combination of the effect of reduced free volume and the interaction energies of PET with LMWDs. A more compatible interaction of PET with acetanilide may require higher activation energy for diffusional jump resulting in more reduction in permeability even though both PET-2.32% phenacetin and PET-1.95% acetanilide showed an equal level of reduction in free volume. Solid-state ¹³C cross polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR) spectra verified a reduction in the localized chain mobility of carbonyl carbon of PET in both PET-2.32% phenacetin and PET-1.95% acetanilide. Furthermore, the dynamic mechanical property measurement in the low temperature region verifies that the presence of LMWDs reduced the low temperature β relaxation in PET.     

Linear thermoelastic characterization of anisotropic poly(ethylene terephthalate) films

All nine independent elastic constants have been determined for a biaxially stretched poly(ethylene terephthalate) (PET) film using novel mechanical methods. The orthotropic directions and the in‐plane Poisson's ratios were first characterized using vibrational holographic interferometry of tensioned membrane samples. The out‐of‐plane Poisson's ratio was obtained by measuring the change in tension with the change in pressure for constant strain conditions. Pressure–volume–temperature (PVT) equipment was used to measure the bulk compressibility as well as the volumetric thermal expansion coefficient (TEC). The in‐plane Young's moduli were obtained by tensile tests, while the out‐of‐plane modulus was calculated from the compressibility and other elastic constants that describe the in‐plane behavior. The in‐plane TECs in the machine and transverse directions were determined using a thermal mechanical analyzer (TMA). The out‐of‐plane TEC was determined using these values and the volumetric TEC determined via PVT. The resulting compliance matrix satisfies all of the requirements of a positive‐definite energy criterion. The procedure of characterization utilized in this article can be applied to any orthotropic film. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2937–2947, 2002     

Grafting of polyacrylamide from poly(ethylene terephthalate) films

Poly(ethylene terephthalate) (PET) films were modified via the grafting of polyacrylamide (PAAM) onto the surface by surface‐initiated atom transfer radical polymerization and UV‐initiated grafting. The surface composition and morphology of the modified PET films were characterized by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and scanning electron microscopy (SEM). The results show that the surface of the PET film was grafted by PAAM, with its own surface morphology different from that of PET. The properties of the modified PET films were studied by contact‐angle, peeling force, penetrability, haze, and friction factor measurements. The results indicate that the peeling force and friction factor of the modified PET films were higher than those of the unmodified PET film. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of the incorporation of saturated fatty acids on the mechanical and barrier properties of biodegradable films

The effects of saturated fatty acids at a concentration of 1.5% on the mechanical and barrier properties of starch‐based films were evaluated in films prepared with two concentrations of glycerol, 20 and 25%. The water vapor permeability (WVP) was determined at three ranges of relative humidity, RH, (0–33, 33–64 and 64–97%). In all cases, an increase in WVP values was observed with increasing RH. SEM images showed a more homogeneous and compact structure in the films with caproic and lauric acids. The films with fatty acids showed higher elongation and maximum stress, and they had Young's modulus values close to those of the control; thus, the addition of fatty acids did not impair the mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structural,mechanical, and gas barrier properties of poly(ethylene terephthalate) nanohybrid using nanotalc

Amorphous poly(ethylene terephthalate) (PET)/nanotalc nanohybrids have been prepared through solution casting route. The fine dispersion of nanotalc clay in the polymer matrix has been examined through transmission electron microscopy (TEM). The intercalation and interaction of nanoclay have further been confirmed using X-ray diffraction, ultraviolet, and Fourier transform infrared techniques. The thermal stability has been tested via thermogravimetric analysis and nanohybrids have been found thermally stable. The glass-transition temperature has been further confirmed through DTA and differential scanning calorimetry analysis which has been increased in the presence of nanotalc arising from greater interaction. The nanohybrids have been tested for their mechanical performances and have been found to have improved mechanical responses for nanotalc-filled nanohybrids. The modulus has been increased whereas toughness has been compromised meagerly. The modulus values have been theoretically predicted using various micromechanical models. The microhardness of the nanohybrids has been examined through Vicker hardness test. The theoretical prediction of the hardness values has been done using different micromechanical models. The structural development upon uniaxial stretching of the samples has been studied using small-angle X-ray scattering and wide-angle ray diffraction. The stretched samples have found to have short-range ordering as well as increased blob size and better coherency in the presence of nanotalc. The aspect ratio has been increased upon stretching. The inclusion of nanotalc has induced high barrier for gas permeation as compared to pure PET. The oxygen transmission rate has been found to decrease up to 64% for 8 wt % of filler concentration. The prediction of the permeability data has been done using different models considering different aspect ratios. The permeability values have been predicted very closely and nanohybrids have been found suitable for practical applications such as packaging. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48607.     

Thermal oxidative degradation kinetics and thermal properties of poly(ethylene terephthalate) modified with poly(lactic acid)

The thermal oxidative degradation kinetics of poly(ethylene terephthalate) (PET) copolymers modified with poly(lactic acid) (PLA) were investigated with thermogravimetric analyzer (TGA). The thermal properties of the modified products were also determined by differential scanning calorimeter (DSC) technique. Waste PET (P100) obtained from postconsumer water bottles was modified with a low‐molecular‐weight PLA. The PET/PLA weight ratio was 90/10 (P90) and 50/50 (P50) in the modified samples. The thermal oxidative degradation kinetics of the modified samples was compared with those of PET (P100). The segmented block and/or random copolymer structure of the modified samples formed by a transesterification reaction between the PLA and PET units in solution and the length of the aliphatic and aromatic blocks were found to have a great effect on the degradation behavior. On the basis of the results of the degradation kinetics determined by Kissinger method, the degradation rate of the samples decreased in the order of P50 > P90 > P100, depending on the amount of PLA in the copolymer structure. However, the degradation activation energies (E_A) of the samples decreased in the order of P100 > P90 > P50. It was concluded that the degradation rate and mechanism were affected significantly by the incorporation of PLA into the copolymer structure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Plasticization of poly(lactide) with poly(ethylene glycol): Low weight plasticizer vs triblock copolymers. Effect on free volume and barrier properties

In order to make poly(lactide) (PLA) suitable for food packaging applications, its toughness must be improved. In this work, the plasticization effectiveness of a low-molecular-weight plasticizer and a triblock copolymer are analyzed. For this purpose, PLA is blended with poly(ethylene glycol) (PEG) and poly(lactide-ethylene glycol-lactide) (LA-EG-LA) triblock copolymer. The obtained results show that copolymers are more effective, reducing the glass transition temperature of PLA. Although PLA/PEG blends have been widely studied in the literature, the barrier character has not been analyzed, which is of paramount importance for packaging applications. Therefore, the permeability to carbon dioxide, oxygen, and water vapor of PLA/PEG blends has been characterized observing an increase with the incorporation of PEG, which is the expected behavior. However, the incorporation of LA-EG-LA copolymers leads to permeability values that are slightly higher, similar, or even lower than PLA. Furthermore, the free volume of the samples has been analyzed in order to gain a deeper insight on the factors affecting the transport properties. Overall, this works aims to provide a better understanding towards the design of biodegradable packaging with improved properties that could be also extended to other biodegradable polymers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48868.     

Mechanical and barrier properties of poly(lactic acid) films coated by nanoclay–ink composition

In this study, poly(lactic acid) (PLA) films were coated by an ink formulation containing nanoclay dispersed with ultrasonic homogenization for 20 min. Mechanical and barrier properties of the coated films were evaluated according to clay type and concentration. PLA films coated by ink formulations containing Cloisite 30B displayed the best mechanical and barrier properties in six types of nanoclays. PLA films coated by Cloisite 30B‐containing ink varying in clay concentration were investigated. Tensile strength and elongation at break of these coated films were improved in 1% Cloisite 30B. Oxygen permeability decreased significantly upon the addition of clay levels up to 1% and slightly decreased with further increases in the amount of the clay. The value of water vapor permeability also decreased depending on the increases of clay (0%–20%). When the clay content in the sample was 2.0%, the surface of coated PLA films displayed aggregation visible using film emission scanning electron microscopy. X‐ray diffractometry and transmission electron microscopy indicated that a mixture of exfoliated and intercalated structure was formed with addition of 1% (w/w) Cloisite 30B to the ink after ultrasonication. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical,barrier, and interfacial properties of biodegradable composite films made of methylcellulose and poly(caprolactone)

Methylcellulose (MC) films were prepared by casting from its 1% aqueous solution containing 0.5% vegetable oil, 0.25% glycerol, and 0.025% Tween^®80. Poly(caprolactone) (PCL) films were prepared by compression molding from its granules. Biodegradable composite films were fabricated using MC film as reinforcing agent and PCL as the matrix material by compression molding. One layer of MC film was reinforced with two layers of PCL films. The MC content in the composites was varied from 10 to 50% by weight. Mechanical, barrier, and degradation properties of PCL, MC, and composite films were evaluated. The values of puncture strength (PS), puncture deformation (PD), viscoelasticity (Y) coefficient, and water vapor permeability (WVP) of the composites (50% MC content) were found to be 124.3 N/mm, 3.2 mm, 31%, and 2.6 g·mm/m²·day·kPa, respectively. Oxygen transmission rate (OTR) of PCL, MC, and composites (50% MC) were found to be 175, 25, 22 cc/m²/d, respectively, which indicated that composite films showed significantly lower OTR than PCL films. Degradation tests of the composite films (50% MC) were performed for 6 weeks in aqueous medium (at 25°C), and it was found that composites lost its mass slowly with time. After 6 weeks, mass and PS of the composites were decreased to 13.4 and 12%, respectively. Composite interface was studied by scanning electron microscopy (SEM). The MC film had good adhesion with PCL matrix during compression molding and suggested strong interface of the composite system. SEM image after 6 weeks of degradation showed some openings in the interface and revealed slow degradation of the MC films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermoluminescence of poly(ethylene terephthalate) films

Thermoluminescence of γ-ray-irradiated poly(ethylene terephthalate) (PET) films in the temperature range from 77K to 300 K is studied. Three glow peaks were observed in this temperature range, at 102 K, 257 K, and 277 K, which preferentially emit at 365, 326, and 304 nm, corresponding to usual fluorescence peaks of normal PET films. The cause may be seen in the self-trapping mechanism which is involved during irradiation of the PET films by γ-rays. A simultaneous observation of the effect of thermal release and photobleaching on thermoluminescence glow intensity supports this mechanism. Energy required to release the electrons from trapping centres also supports this observation.     

Stereocomplex‐induced gelation properties of polylactide/poly(ethylene glycol) diblock and triblock copolymers

The ring‐opening polymerization of L ‐ or D ‐lactide was realized in the presence of dihydroxyl or monomethoxy poly(ethylene glycol) (PEG) with a number‐average molecular weight of 2000. The resulting low‐molar‐mass poly(L ‐lactide) (PLLA)/PEG and poly(D ‐lactide) (PDLA)/PEG triblock and diblock copolymers were characterized with nuclear magnetic resonance (NMR), differential scanning calorimetry, size‐exclusion chromatography, and X‐ray diffractometric analysis. Bioresorbable hydrogels were successfully prepared from aqueous solutions containing both copolymers because of interactions and stereocomplexation between the PLLA and PDLA blocks. Gelation was evaluated with the tube inverting method and rheological measurements. A phase diagram was realized with gel–sol transitions as a function of concentration. The rheological properties of the hydrogels were investigated under various conditions through changes in the copolymer concentration, temperature, time, and frequency. It was concluded that the hydrogels constituted a dynamic and evolutive system because of the continuous formation/destruction of crosslinks and degradation. Further studies are underway to elucidate the degradation behavior and the potential of these substances as drug carriers or cell culture scaffolds. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011