Hydrophobic Zeolite‐Filled Polymeric Films with High Ethylene Permselectivity for Fresh Produce Packaging Applications

Gas permselective plastic films have been in a great deal of attention in the area of modified atmosphere packaging of fresh produces. Such films must allow transport of the respiring gases, i.e. oxygen and carbon dioxide, in a controlled manner and, moreover, should efficiently remove ethylene gas. Therefore, the development of highly permeable films with high ethylene permselectivity, i.e. high in both permeability and selectivity, was carried out. The concept of ‘mixed matrix membrane’, by which enhanced gas permselectivity can be obtained by incorporation of zeolite particles into the polymeric film, was applied. Fine particles of hydrophobic zeolites, i.e. zeolite beta and ZSM‐5, and the surface‐modified zeolites were used in this study. The films with uniform distribution of zeolite particles (10% w/w) in 70LDPE/30SEBS (styrene‐b‐(ethylene‐ran‐butylene)‐b‐styrene block copolymer) matrix can be prepared by blow film extrusion. Significantly high ethylene permselectivity, i.e. ethylene permeability of 1.78–2.67 × 10³ cm³ ? mm/m² ? day ? atm and ethylene/O₂ selectivity of 4.67–8.26, was obtained from the films containing octyl‐modified and phenyl‐modified zeolites. Particular enhancement was observed on the films containing phenyl‐modified zeolites. Crystallinity of polyethylene, transition temperatures and decomposition temperature were, however, indifferent among the studied films. Nevertheless, elongation at break and toughness of the films containing surface‐modified zeolites were superior. Particle–polymer interface could thus be improved. Copyright © 2014 John Wiley & Sons, Ltd.     

Linear and non-linear viscoelastic behaviors of crosslinked tapioca starch/polysaccharide systems

Effects of polysaccharides on both the thickening performance and large deformation behavior of mixtures of various crosslinked tapioca starch and polysaccharide were investigated. It was found that the gelatinized crosslinked tapioca starch at 1-8% w/w in aqueous solutions behaved as swollen granules with the low-shear viscosity described by Krieger & Dougherty equation. To achieve thickening performance, 3.5% w/w starch was cooked with a range of 0.5% w/w polysaccharides, i.e. konjac glucomannan, guar gum, xanthan gum, and their 50:50 mixtures. It was shown that additions of polysaccharides greatly affected the rheological behavior of the suspensions, predominantly in the linear viscoelastic regime. The studied mixtures of starch and polysaccharides exhibited strong synergistic effects as evidenced from the increase in their consistency coefficients and the excess storage moduli calculated from the Palierne equation. Moreover, the mixtures containing xanthan gum showed weak-gel characteristics while the others demonstrated liquid-like behavior. In the non-linear viscoelastic analysis, arrangement of starch granules and specific interfacial interactions evidently affected the deformation behavior of the mixtures of crosslinked tapioca starch and polysaccharide. The mixture of konjac glucomannan and xanthan also largely improved stress susceptibility of the suspension and gave the unique shear stiffening under large amplitude oscillatory shear experiment.     

Compatibilization of high‐impact polystyrene/high‐density polyethylene blends by styrene/ethylene–butylene/styrene block copolymer

Compatibilization of polymer blends of high‐impact polystyrene (HIPS) and high‐density polyethylene (HDPE) blend by styrene/ethylene–butylene/styrene (SEBS) was elucidated. Polymer blends containing many ratios of HIPS and HDPE with various concentrations of SEBS were prepared. The Izod impact strength and elongation at break of the blends increased with increases in SEBS content. They increased markedly when the HDPE content was higher than 50 wt %. Tensile strength of blends increased when the SEBS concentration was not higher than 5 pphr. Whenever the SEBS loading was higher than 5 pphr, the tensile strength decreased and a greater decrease was found in blends in which the HDPE concentration was more than 50 wt %. The log additivity rule model was applied to these blends, which showed that the blends containing the HIPS‐rich phase gave higher compatibility at the higher shear rates. Surprisingly, the blends containing the HDPE‐rich phase yielded greater compatibility at the lower shear rates. Morphology observations of the blends indicated better compatibility of the blends with increasing SEBS concentration. The relaxation time (T₂) values from the pulsed NMR measurements revealed that both polymer blends became more compatible when the SEBS concentration was increased. When integrating all the investigations of compatibility compared with the mechanical properties, it is possible to conclude that SEBS promotes a certain level of compatibilization for several ratios of HIPS/HDPE blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 742–755, 2004     

Argon Plasma Treatment of Tapioca Starch Using a Semi-continuous Downer Reactor

To develop a novel modification process of tapioca starch using low-pressure argon plasma treatment in a large-scale production, a semi-continuous downer reactor was designed to provide a production rate of 0.1–0.5 kg per cycle. Physicochemical and rheological properties of plasma-treated starch were investigated in order to predict the phenomena occurred during the plasma treatment. Native tapioca starch (NTS) was plasma-treated for 1, 3, or 6 cycles, which were referred to as PTS-1, PTS-3, or PTS-6 samples, respectively. Plasma treatment of the NTS resulted in a significant decrease (P?<?0.05) in paste clarity and Rapid Visco Analyzer (RVA) breakdown viscosity, and an increase in gel strength of starch. The PTS-1 had the lowest paste clarity of 39.85 %T at 650 nm and breakdown viscosity of 29.71 Rapid Visco Unit (RVU), and the highest gel strength, e.g., G′?=?5.47ω ^0.32. With increasing the number of treatment cycles, i.e., the PTS-3 and PTS-6, the paste clarity and breakdown viscosity significantly increased (P?<?0.05), while the gel strength decreased. The Fourier transform infrared (FTIR) spectroscopy via relative areas of C–O–C peaks indicated that the PTS-1 had a significant increase (P?<?0.05) in the C–O–C cross-linked bonds compared to the NTS, but the effect of depolymerization could further suppress the cross-linking reaction when the number of treatment cycle was increased. Taking an advantage of a very short residence time (less than 0.3 s) in the plasma downer reactor, the semi-continuous process of starch modification could be developed for a commercial production of non-chemically modified starch with a relatively low degree of cross-linking.     

Physicochemical and rheological characteristics of commercial chili sauces as thickened by modified starch or modified starch/xanthan mixture

Physicochemical and rheological properties of various commercial chili sauces were characterised in this study. It was found that all studied sauces were acidic. Fourier transform infrared spectroscopy and colour staining experiments showed that the studied sauce could be categorised into two groups: one containing only starch and the others having both starch and xanthan within their ingredients. The rheological measurements showed that all sauces had a weak gel-like characteristic with strong shear thinning behaviour. In particular, the sauce with the weakest network contained only starch. Flow experimental data, fitted with the Herschel-Bulkley model, also revealed that the sauce with the lowest total solid content had undetectable yield stress, the lowest consistency coefficient, and the highest flow behaviour index, hence the weakest network structure amongst the studied sauces. The xanthan-starch mixture was shown to be beneficial as they could interact synergistically in acidic condition to enhance the gel-like characteristics and shear thinning behaviour of chili sauces.     

Effects of cross-linked tapioca starches on batter viscosity and oil absorption in deep-fried breaded chicken strips

In this study, the effectiveness and feasibility of using various degrees of cross-linked tapioca starches in batter and breading formulations to reduce oil absorptions in deep fried chickens were investigated. Shear flow behaviour, water retention capacity (WRC), pick-up as well as cooked yield of the prepared batters were also examined. Flow curves showed that all studied batters were pseudoplastic, i.e. having shear thinning characteristics. In addition, it was found that the substitution of 20% (w/w) cross-linked starches for wheat flour in the batter formulation significantly reduced the consistency index and WRC of the batters. However, batter pick-up and cooked yield values were insignificantly affected. Oil uptake of fried chicken crusts was determined using differential scanning calorimetry due to its specific advantages over the conventional solvent extraction method. In comparison to the control (wheat) formulation, crusts of fried chicken samples obtained from the formulations containing 20% (w/w) cross-linked starch showed significantly lower oil content by at least 17% relative oil reduction. The highest relative oil reduction was found in the batter containing the highly cross-linked tapioca starch. Furthermore, an increase in water content in the batter formulations resulted in a reduction in the batter pick-up, cooked yield and oil absorption. The degree of cross-linking which in turn resulted in the limited starch granule disintegration is the predominant factor in the reduction of oil content for deep-fried battered food.     

Selective ethylene‐permeable zeolite composite double‐layered film for novel modified atmosphere packaging

The composite double‐layered films, for the packaging application of postharvest fruits and vegetables, were prepared by laminating low‐density polyethylene (LDPE) and poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) modified with zeolite ZSM‐5. The film was characterized by scanning electron microscope and differential scanning calorimeter and tested for permeation of ethylene (C₂H₄), oxygen (O₂), carbon dioxide (CO₂), and water vapor. It was found that the C₂H₄ permeability of the films was improved because of an enhanced adsorption of C₂H₄ by the incorporated zeolite (0–10 wt%). The preconcentrated layer (zeolite/SEBS) leads to a higher C₂H₄ concentration gradient across the film. Moreover, the high dispersion of zeolite increased the C₂H₄ permeation. When compared with O₂ and CO₂, the composite films were more selective to C₂H₄. However, the C₂H₄ permeation decreased in the presence of O₂ because of a competitive adsorption. In addition, the films possessed appreciate tensile properties for packaging application. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Rheological investigation of cure kinetics and adhesive strength of polyurethane acrylate adhesive

In this work, we used rheological techniques to study both the cure characteristics and the degree of cure of polyurethane acrylate adhesive, a type of reactive adhesive used in hard disk component assembly. These results were then correlated with the tensile shear strengths of adhesives. Here, the cure characteristics of polyurethane adhesive were investigated at isothermal conditions ranging from 25 to 120°C. From the rheological results, the gelation time, the vitrification time, as well as the time required to reach the maximum degree of cure, decreased when increasing the curing temperature. The cure rates of adhesive increased with temperature in three temperature ranges, which were retardation zone, vitrification zone, and reaction‐controlled zone. The cure rates in these zones were controlled by slow diffusion, fast diffusion, and the rate of reaction, respectively. From the temperature sweep of fully‐cured adhesives, we found that the crosslinking level of adhesives increased with curing temperatures at different rates depending on the temperature zones as well. Moreover, the adhesive strength measured by tensile shear test was found to also increase correspondingly with the adhesives' T_g, indicating that the crosslinking level directly affected the adhesive strength. The strong dependence of adhesive strength with crosslinking level indicates that the crosslinking level was essential for high adhesive strength. The correlation of cure characteristics and adhesive strengths at various curing temperatures performed in this study can further provide useful information for planning appropriate curing schemes of polyurethane acrylate adhesives used in electronic and other industries. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of Freezing Rate and Starch Granular Morphology on Ice Formation and Non-Freezable Water Content of Flour and Starch Gels

Ice formation and non-freezable water (W_NFW) of rice flour and tapioca starch gels were studied at two different freezing rates (–10 and –100°C/min) using differential scanning calorimetry. Ice crystal growth was observed in the slow freezing but not in the fast one. Ice melting enthalpies, however, were similar since more ice formed in holding and reheating steps. Melting enthalpy of fully gelatinized systems with water contents ~ 0.50–0.66 was associated to starch composition and granule morphology. Highly swollen tapioca starch gave the lowest enthalpy and the highest W_NFW (0.40 g/g dry starch versus 0.32 and 0.38 g/g dry starch of normal and waxy rice flours, respectively). The further studies revealed that the W_NFW values were associated to swelling power, solubility, and granule morphology.     

Comparison of Various Packaging Films for Mango Export

This study compared the effects of the use of various types of packaging films in maintaining quality, preserving bioactive compounds and extending shelf life of the ‘Nam Dok Mai’ mango. The principal techniques for maintaining the quality of mangoes are based on modified atmosphere packaging using highly gas‐permeable films and an ethylene‐removing mechanism. The films studied were non‐perforated highly gas‐permeable film, non‐perforated ethylene‐absorbing highly gas‐permeable film (HNPE), micro‐perforated highly gas‐permeable films (HMP) and common non‐perforated polyethylene film (LNP). These films were compared with non‐packaging treatment, which served as a control (C). Gas composition (O₂, CO₂ and C₂H₄) in the package headspace was monitored during storage at 12°C. The quality of mangoes were assessed by weight loss, colour (L* a* b*), texture, total soluble solids, titratable acidity, total phenolics, total flavonoids, ethanol concentration and sensory quality. Equilibrium‐modified atmospheres of 5 kPaO₂ + 5 kPaCO₂ and 4 kPaO₂ + 5 kPaCO₂ were achieved in the non‐perforated highly gas‐permeable film and HNPE packs, respectively. Carbon dioxide accumulation was observed in the HMP and LNP packs where CO₂ reached 17 and 10 kPa, respectively, after storage for 10 days. The shelf life of mangoes was extended to 40 days with HNPE, 35 days with HNP, and 30 days with HMP, as compared with 20 days with control and 5 days with LNP. HNPE, the film incorporated with fine particles of mordenite framework inverted‐type zeolite with ethylene‐absorbing ability, could further extend the shelf life of mangoes in addition to modified atmosphere packaging alone. Copyright © 2011 John Wiley & Sons, Ltd.