Natural Antimicrobial – Containing EVOH Coatings on PP and PET Films: Functional and Active Property Characterization

Natural antimicrobials are currently being tested by many researchers for active packaging applications as a response to consumer demands for safer food products. In previous work, several packaging materials consisting of ethylene vinyl alcohol (EVOH)‐coated polypropylene (PP) films containing essential oils or their constituents as active agents were successfully developed and tested for antimicrobial activity. In this work, selected films from those materials, namely EVOH coatings with carvacrol, citral, marjoram essential oil, or cinnamon bark essential oil, on PP and polyethylene terephthalate (PET) substrates, were subjected to diverse physicochemical analyses in order to assess their suitability for food packaging applications. Concretely, the investigated properties were the stability of EVOH coatings on PP and PET substrates, the retainability of EVOH matrices for active compounds, the mechanical, optical, surface and barrier properties of the final active films and the effects of a matrix modification based on the addition of bentonite nanoclay on the performance of PP/EVOH active packages studied in actual working conditions. Results showed that the application of corona discharge followed by a polyethyleneimine‐based primer was the best anchorage treatment available to stabilize EVOH coatings on PP and PET substrates. Furthermore, they demonstrated that the retention of active agents into EVOH matrices ranged from low to moderate, depending on the embedded substance, and that their presence into an EVOH coating in the final multilayer films did not noticeably affect their mechanical, optical or barrier properties, although it considerably improved their wettability. They also indicated that the inclusion of bentonite nanoparticles into their carrier layers substantially enhanced the performance of the final packages, while maintaining or slightly improving their other physical properties. Hence, as a conclusion, all the assayed multilayer films were considered perfectly valid for food packaging applications, and the incorporation of bentonite nanoclay to their carrier layers was also highly recommended. Copyright © 2014 John Wiley & Sons, Ltd.     

EVOH Films Containing Antimicrobials Geraniol and α‐Terpilenol Extend the Shelf Life of Snakehead Slices

Various studies have provided information on active packaging to prevent food putrefaction effectively . In this work, ethylene–vinyl alcohol copolymer (EVOH) films with geraniol (Ger) and α‐terpilenol (Ter) were successfully prepared by extrusion. The mechanical, thermal, oxygen barrier and antimicrobial properties of the packaging films were characterized, and the application of the films in snakehead preservation was examined. Thermogravimetric analysis showed that the addition of Ger and Ter did not decrease the films properties but improved their oxygen barrier property and thermostability. Moreover, the incorporation of Ger and Ter inhibited the growth of Escherichia coli, Salmonella enterica and Listeria monocytogenes. Both of the films, EVOH/Ger (EVOH/Ger) and EVOH/Ter (EVOH/Ter), reduced Salmonella enterica by 2.36 ± 0.17 and 1.91 ± 0.06 log units, respectively. Meanwhile, the effects of EVOH/Ger and EVOH/Ter on quality assessment of snakehead slices were examined through sensory tests and analyses of biochemical indices during refrigerated storage (4°C ± 1°C) for 10 days. Sensory properties, total viable counts, total volatile basic nitrogen, thiobarbituric acid and pH values were evaluated. On eight day, compared with the control fish samples, the total viable counts and total volatile basic nitrogen values cut down 1.98 ± 0.02 log units and 11.3 ± 0.11 mgN/100 g, respectively, for fish samples packaged by EVOH/Ger. The active films containing 6% (wt) Ger and 6% (wt) Ter inhibited the growth of E. coli, S. enterica and L. monocytogenes and effectively extended shelf life by 4–5 days under cold‐storage conditions compared with the control group. Copyright © 2017 John Wiley & Sons, Ltd.     

Effect of high‐pressure food processing on the mass transfer properties of selected packaging materials

The effect of high‐pressure processing (HPP) on the total migration into distilled water and olive oil and on the barrier properties of four complex packaging materials were evaluated. The films were polyethylene/ethylene‐vinyl‐alcohol/polyethylene (PE/EVOH/PE), metallized polyester/polyethylene, polyester/polyethylene (PET/PE), and polypropylene‐SiOx (PPSiOx). Pouches made from these films were filled with food simulants, sealed and then processed at a pressure of 400 MPa for 30 min, at 20 or 60°C. Pouches kept at atmospheric pressure were used as controls. Prior to and after treatment, all films were evaluated for their barrier properties (oxygen transmission rate and water vapour transmission rate) and ‘Total’ migration into the two food simulants. In the case of water as the food stimulant, a low ‘Total’ migration was observed and even a lower one after the HPP treatment. In the case of oil as the food simulant, a higher ‘Total’ migration was found compared to the control as a result of damage to the structures during the HPP treatment. The gas permeability of the films increased after the HPP, compared to the control, due to damages in the structure caused during the treatment. The PET/PE film presented minimum changes in properties after HPP. Copyright © 2010 John Wiley & Sons, Ltd.     

The effect of high‐pressure food processing on the sorption behaviour of selected packaging materials

The sorption behaviour and flavour‐scalping potential of selected packaging films in contact with food simulant liquids (FSLs) (ethanol and acetic acid solutions) were evaluated after high‐pressure processing (HPP). The films used were monolayer polypropylene (PP), a multilayer (polyethylene/nylon/ethylene vinyl alcohol/polyethylene: PE/nylon/EVOH/PE), film and a metallized (polyethylene terephthalate/ethylene–vinyl acetate/linear low‐density polyethylene: metallized PET/EVA/LLDPE) material. D‐limonene was used as the sorbate and was added to each of the FSLs. After HPP treatment at 800 MPa, 10 min, 60°C, the amount of D‐limonene sorbed by the packaging materials and the amount remaining in the FSL was measured. Untreated controls (1 atm, 60°C and 40°C) were also prepared. Extraction of the D‐limonene from the films was performed using a purge/trap method. D‐limonene was quantified in both the films and the FSL, using gas chromatography (GC). The results showed that D‐limonene concentration, in both the films and the food simulants, was not significantly affected by HPP, except for the metallized PET/EVA/LLDPE. Significant differences in D‐limonene sorption were found in comparison with the control pouches. The results also showed that changes in temperature significantly affected the sorption behaviour of all films. Copyright © 2004 John Wiley & Sons, Ltd.     

丁香精油食品抗菌包装材料的制备及性能研究

目的以壳聚糖为基材与丁香精油相结合制备可食性抗菌包装。方法先制备膜,再根据检测膜的厚度、力学性能、抑菌性能来确定各成分的添加量,确保膜各方面的性能处于最优状态。结果当甘油的质量分数为1.0%,壳聚糖的质量浓度为20 mg/m L,丁香精油的质量分数为1.0%时,丁香精油壳聚糖抗菌包装膜具有最好的力学性能和抑菌性能。结论丁香精油食品抗菌包装材料的制备需要结合膜的性能来确定最终成分的含量,以达到最优的设计。     

Mechanical and thermal behaviour of flexible food packaging polymeric films materials under high pressure/temperature treatments

The effect of high‐pressure processing on mechanical and thermal properties of four complex packaging materials (polyethylene/ethylene vinyl alcohol/ polyethylene: PE/EVOH/PE; metallized polyester/polyethylene: PETmet/PE; polyester/polyethylene: PET/PE; polypropylene SiOx recovered: PPSiOx) was studied. Pouches of the different materials containing distilled water or olive oil as food simulants, as well as empty ones, were subjected to 400 MPa for 30 min, at temperatures of 20 or 60°C. Delamination and wrinkling were a general consequence of the high‐pressure processing of multilayer polymeric systems. However, no significant changes were observed regarding the mechanical properties of PE containing laminates after pressurization. PPSiOx underwent significant modifications as SiOx completely broke down. Neither thermal property was affected by pressure, as it was the processing temperature that induced tempering effects on the crystallization behaviour of polymeric components. Only PE/EVOH/PE, when in contact with water as a simulant, presented a decrease in the melting point temperature. Copyright © 2008 John Wiley & Sons, Ltd.     

Influence of high‐pressure processing on selected polymeric materials and on the migration of a pressure‐transmitting fluid

This study investigated the migration of 1,2‐propanediol (PG) through selected food packaging films exposed to high‐pressure processing (HPP). Pouches made from these materials were filled with 95% ethanol as a food‐simulating liquid. These packages were then processed using a pilot‐scale high‐pressure food processor at 400, 600 and 827 MPa and 30, 50 and 75°C for 10 min. Controls were processed at similar temperatures and times, but at atmospheric pressure. To investigate any structural changes to these films during HPP, water was used as the food simulant at temperatures of 30, 75, 85, 90 and 95°C and at pressures of 200, 400, 690 and 827 MPa. No detectable PG migration into the polyester/nylon/aluminium (Al) polypropylene (PP) meal‐ready‐to eat (MRE)‐type pouches was observed. PG migration into the nylon/ethylene vinyl alcohol (EVOH)/PE (EVOH) pouches was similar at 30, 50 and 75°C after 10 min under atmospheric pressure. However, PG migration into the EVOH pouches significantly decreased when treated with high pressure at 30, 50 and 75°C. At 75 and 50°C, the PG migration was significantly higher than the amounts detected at 30°C. Visible signs of delamination between the polypropylene (PP) and aluminum (Al) layers were observed in the MRE pouches processed at ≥200 MPa and 90°C for 10 min. This delamination appeared to occur between the PP and Al layers. The differential scanning calorimetric analyses and Fourier transform infrared (FTIR) spectra were similar for the high‐pressure treated pouches when compared to their respective controls. This indicated that there were no HPP‐induced molecular changes to the treated pouches. Results from this study should be useful to HPP users for predicting PG migration trends and in deciding the selection of appropriate packaging materials for use under similar processing conditions. Copyright © 2002 John Wiley & Sons, Ltd.     

PLA/PBSA 纳米活性包装薄膜的性能研究

目的研究可降解材料聚乳酸(PLA)/聚丁二酸丁二醇酯-聚己二酸丁二醇酯共聚物(PBSA)薄膜在添加有机纳米蒙脱土(MMT)和精油后的抗氧化性和保鲜性能。方法采用挤出共混改性和挤出流延法加工制备出PLA/PBSA/MMT/精油纳米复合薄膜,对其力学性能、透湿性、透气性、抗氧化性等进行探讨,并研究对樱桃的保鲜作用。结果添加了DK4型号MMT的PLA/PBSA薄膜的抗拉强度得到提高,薄膜的水蒸气透过率、透气率得到降低,但是对樱桃保鲜的各项指标与对照组无明显差异。在此基础上添加丁香精油后,力学性能得到提升,抗氧化作用明显,并且对改善樱桃的保鲜效果显著增加。结论添加了DK4型MMT和丁香精油的PLA/PBSA薄膜有着较好的改性效果,并且有良好的保鲜效果。     

Influence of composition on structure and barrier properties of active PET films for food packaging applications

A very attractive solution in food packaging technology is the functionalization of packaging materials by incorporating an active phase into polymeric matrices. Nowadays, the applications of active substances into flexible packaging are very limited due to difficulties in realizing performing films by common manufactory processes. This work is focused on the production and characterization of monolayer poly(ethylene terephtalate) (PET) active films at different concentrations of an oxygen scavenger by cast extrusion process. Rheological, thermal, morphological analyses and oxygen absorption measurements were carried out on the produced samples to investigate the structure of active PET films and to determine their scavenging properties. Overall migration analyses were performed on active films to asses their safety in use with foodstuff, and finally the produced films were used to package fresh banana slices for evaluating their capability in quality foods preservation. Copyright © 2010 John Wiley & Sons, Ltd.     

Blending and oxygen permeation properties of the blown films of blends of modified polyamide and ethylene vinyl alcohol copolymer with varying vinyl alcohol contents

The oxygen permeation and blending properties of the MPAEVOH blends of modified polyamide (MPA) and ethylene vinyl alcohol copolymer (EVOH) with varying vinyl alcohol contents were systematically investigated in this study. The oxygen permeation rates of EVOH film specimens are dramatically slower than that of the PE specimen and reduce significantly as their vinyl alcohol contents increase. After blending EVOH in MPA resin, the oxygen permeation rates of each MPAEVOH series film specimens reduce significantly as their EVOH and/or vinyl alcohol contents increase, respectively. At some optimum compositions, the oxygen permeation rates of the MPAEVOH film specimens are even lower than that of the pure EVOH film specimen with a vinyl alcohol content of 52 wt%. On the other hand, the average radius (R _f), volume (V _f) of the free-volume-cavities and fractional free-volume (F _v) values of each MPAEVOH series specimens reduce significantly as their EVOH and/or vinyl alcohol contents increase. These interesting barrier and free-volume properties of the EVOH and MPAEVOH specimens with varying vinyl alcohol contents were investigated in terms of the intermolecular interaction and/or free-volume properties in the amorphous phases of the EVOH and MPAEVOH specimens obtained in this study.     

Potential of migration of active compounds from protein‐based films with essential oils to a food and a food simulant

Migration tests at different temperatures and storage periods were performed to evaluate the release of active compounds from active whey protein films (WPFs) to a food and food simulants. Whey protein film incorporated with different levels of an optimized essential oils (EOs) blend (1%, 2%, 2.7%, and 5%, w/w) were prepared by casting. This blend contained EOs from rosemary and 2 species of cinnamon. Salami was packaged with WPF and stored during 180 days at 5°C. Temperature influenced significantly the migration of compounds (P<.1). It was observed that eucalyptol was the compound that presented the highest potential of migration into 95% ethanol (v/v). After contact of film with salami, it was observed that, in general, more than 50% of active compounds released from WPF to salami. It was observed that higher amounts of active compounds were released to salami than to fatty food simulant. Results suggested that the release of compounds depends on their affinity with the food/food simulant, temperature, their concentration in packaging, and composition of food. Active packaging may ensure the quality of food due the migration of compounds from EO with antimicrobial and antioxidant activity incorporated in the film to the foodstuff.     

丁香精油等改性PE膜及其对抑菌保鲜性能的影响

目的研究经丁香精油等抗菌、抗氧化剂改性的聚乙烯(PE)薄膜的物理性能和保鲜性能。方法利用丁香精油、乙二胺四乙酸二钠(EDTA-2Na)和维生素E改性PE树脂,并对成形后的改性PE膜进行相应性能的测试和分析。结果丁香精油具有较好的抑菌效果,最佳质量分数为5%;以维生素E复合EDTA-2Na为抗氧化剂,维生素E质量分数为2%,EDTA-2Na质量分数为1%时,取得了良好的抗氧化结果。精油和抗氧化剂的添加提高了PE膜的刚性与阻隔性。结论经丁香精油、维生素E和EDTA-2Na改性的PE薄膜具备一定的抑菌性、抗氧化性,且其水蒸气和氧气的阻隔性能也得到了改善。经丁香精油、维生素E、EDTA-2Na(质量分数分别为5%,2%,1%)改性的PE薄膜能有效延长草莓的货架期。     

A simple model for the interaction between water vapour and oxygen transmission in multilayer barrier materials intended for food packaging applications

The low oxygen permeability of the ethylene‐vinyl alcohol copolymer, EVOH, is outstanding, but is also known to be very sensitive to moisture uptake and cannot be used as a monolayer packaging material. In this paper, theory is presented in order to calculate the average water activity of the EVOH layer at steady state and the corresponding oxygen barrier for different multilayer structures using various polymer types and layer thicknesses. Multilayer materials can be designed for different food packaging applications and storage conditions, in order to keep the relative humidity of the barrier below recommended 75%, by varying the thickness of the outside versus the inside protective layers and/or varying the water vapour transmission rate of the outside versus the inside layer. The conclusion reached is that to retain the optimal barrier properties and thereby the optimal protection of the food, asymmetric multilayer structures are necessary. Copyright ©2007 John Wiley & Sons, Ltd.     

抗菌活性包装膜及其控释技术的研究进展

目的为控释型抗菌活性包装膜在食品工业中的应用与开发研究提供基础。方法综述抗菌活性包装膜及其结合控释技术的国内外研究进展,同时总结抗菌活性包装膜在果蔬类、动物源类食品中的应用,并对控释型抗菌活性包装膜未来的发展趋势进行展望。结果抗菌活性膜与控释技术相结合的研究还处于起步阶段,其抗菌剂的选择、安全性、物理性质、释放规律等问题还需深入研究。结论国内外抗菌薄膜的实验室研究阶段基本成熟,但是在结合控释技术的应用方面还有待进一步推广,因此,开发安全、高效的控释型抗菌活性包装膜和推广食品包装应用是食品包装技术的研究方向。     

Antioxidant Effects of Sesamol Released from Polymeric Films on Lipid Oxidation in Linoleic Acid and Oat Cereal

The antioxidant effects of sesamol films were evaluated using a food simulant (linoleic acid) and a real food (oat cereal). Sesamol was melt blended with high density polyethylene, linear low density polyethylene and ethylene‐vinyl acetate resins using co‐extrusion to produce sesamol films of multilayer structure; for comparison, films containing butylated hydroxytoluene (BHT) or no additive (as control) were also produced. At least 60% of the initial amount of sesamol remained in the films after extrusion. The release of sesamol from the sesamol films was about six times faster at 30°C than at 10°C. The antioxidant effectiveness of sesamol and BHT was evaluated on the basis of induction period of lipid oxidation, conjugated dienes (for linoleic acid), hexanal (for oat breakfast) and sensory evaluation. Compared with the control film, the sesamol films extended the induction period of linoleic acid by five and eight times at 40°C and 23°C, respectively. After 12 month storage at 23°C, hexanal formation was 59% less in cereal packaged with sesamol films than that packaged with control film. Rancid odours were detected in cereal packaged with control films, but not with sesamol or BHT films. The incorporation of sesamol had only slight effects on tensile properties and transparency. Copyright © 2012 John Wiley & Sons, Ltd.     

New functionalized ethylene/vinyl alcohol co-polymers:synthesis and water vapour transport properties

An ethylene/vinyl alcohol co-polymer (EVOH) has been chemically modified to induce the formation of ionic clusters. –COOH containing pendant groups have been grafted on the polymer backbone and subsequently have been partially or totally salified. The structure of this class of polymers is expected to be less sensitive to the effect of water vapour if ionic concentration is above a threshold value which guarantees the formation of ionic aggregates. Moreover, the presence of ionic couples should guarantee an increased compatibility towards other polymers if compared to EVOH. Water vapour transport properties of functionalized EVOHs have been determined in order to assess the effect of chemical modifications both on water barrier properties and on sensitivity of polymer structure to sorbed water. Water vapour sorption tests have been performed at 35°C at several water vapour activities determining both water sorption isotherms and diffusivities. This is a preliminary study on this new class of materials aimed to assess the possible replacement of EVOH films (or EVOH containing multilayer films) with films based on such polymers (or their blends with other polymers) which should be characterized by a higher resistance to ‘retorting’ conditions. © 1997 John Wiley & Sons, Ltd.     

Preparation and properties of quercetin‐incorporated high density polyethylene/low density polyethylene antioxidant multilayer film

High density polyethylene/low density polyethylene (LDPE) antioxidant multilayer films were prepared by the co‐extrusion method, and quercetin was incorporated in the LDPE layers as an antioxidant. The release rates of quercetin and the antioxidant activities of films were adjusted by changing the amount of ethylene vinyl acetate (EVA) and diatomite added into the LDPE active layer. The morphologies of the films were observed by SEM, and the release property of quercetin was characterized by a high‐performance liquid chromatography (HPLC) method. The mechanical properties and heat sealing performance of the films were influenced to a certain extent by the amounts of EVA and diatomite in the active layers, while the barrier properties of the films were almost unchanged. The release of quercetin from the active films to a food simulant (95% alcohol) at 37°C was measured over 55 days. When the EVA amounts were 30% and 40% to 50%, the diffusion coefficients, D, were 10^?14 and 10^?13 cm²/s, respectively. In addition, the antioxidant activity values of the films were enhanced as the EVA amount increased. When adding diatomite into the active layer with 50% EVA, the diffusion coefficient, D, was 10^?11 cm²/s, and the quercetin was almost completely released with a partition coefficient, K, of less than 1. Meanwhile, the antioxidant activity values of the films exceeded 95%. The antioxidant release rate could be adjusted within a wide range; thus, these active films could be used for food antioxidant protection.     

Role of package headspace on multilayer films subjected to high hydrostatic pressure

The objective of this study was to systematically examine the effect of high‐pressure processing and package headspace on package integrity and properties. Working pressures were 400 and 600 MPa, and starting vessel temperatures were 30°C, 60°C, and 90°C. Coextruded and laminated multilayers packaging films were studied: film A: (PA/EVOH/PP) and film B: (PET‐AlO_x‐OC/PA6/PP), respectively. The films were made into pouches (0.05 m × 0.10 m) and filled with 30‐mL water as a model food. Various headspace volumes (0, 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30‐cc air/mL H₂O) were introduced into the packaging before processing. Imaging was used to quantify defects such as the formation of white spots on the package surface and delamination of film layers. The results showed that the headspace level and processing initial temperature had a greater effect than the operating pressure on visual defects. The package with 0% headspace did not show any physical damage to the tested films. Furthermore, thermal and mechanical analyses showed that the coextruded film A had better resistance to testing conditions than the laminated structure of film B. The X‐ray diffraction results showed that film B had more defects than film A that altered the crystalline structure. Visual observation revealed white spots and delamination in the inside layer (PP) in both films. The same processing conditions affected the oxygen and water vapour transmission rates of film B more than film A. This work provides a basic guideline to select the right headspace for a given type of packaged food whenever heat and pressure are used simultaneously.     

Effect of active films incorporated with montmorillonite clay and α‐tocopherol: Potential of nanoparticle migration and reduction of lipid oxidation in salmon

Fat‐rich fish such as salmon are highly susceptible to lipid oxidation, which affects the quality of the product. The compound α‐tocopherol is widely used as an antioxidant added directly to food or through the incorporation in active packaging besides having activity of vitamin E, which is an essential nutrient to the human body absorbed from food. The objective of this paper was to evaluate the montmorillonite (MMT15A) and α‐tocopherol migration potential and antioxidant effect of chitosan/MMT15A/α‐tocopherol active films on reduction of lipid oxidation in fresh salmon. Chitosan films incorporated with MMT15A (0 and 1 g/100 g) and α‐tocopherol (0, 10, and 15 g/100 g) were applied on the fresh salmon for 8 days. Samples of salmon wrapped in films 3 and 6 (10% tocopherol and 1% MMT15A + 15%tocopherol, respectively) showed the lower values of thiobarbituric acid reactive substances (TBARS) at eighth storage day at 4°C. Film 6 (1% MMT15A and 15% tocopherol) showed better result on reduction in water vapour transmission rate (WVTR) and controlled release of tocopherol. All the films containing MMT15A presented migration of minerals (Mg and Si) for the salmon during the 8 days. Thus, the use of this film for release of active substances is a promising alternative for application as food packaging in order to obtain nutritionally fortified foods and inhibit oxidation reactions.     

聚乙烯醇/蒙脱土/山梨酸钾活性包装膜制备及释放

目的 通过制备聚乙烯醇（PVA）/蒙脱土（MMT）/山梨酸钾活性包装膜,考察其包装性能及山梨酸钾在膜材内的释放效果。方法 通过流延法制备含有不同浓度MMT的聚乙烯醇/山梨酸钾活性包装膜,分析活性包装膜的色度、透明度、拉伸性能和含水量,同时研究山酸钾在活性膜内向脂肪性食品模拟物中的释放行为。结果 通过添加MMT改善膜材的包装性能,MMT的添加在显著提高PVA膜拉伸强度的同时还降低了PVA膜的断裂伸长率,加深了膜材的色度,降低了膜的透明度;PVA膜的含水率随着MMT浓度的提高而降低。MMT的添加可明显改变山梨酸钾向脂肪类模拟物的释放行为,当MMT的质量分数为2%时明显地降低了山梨酸钾的释放量。结论 通过调整膜内MMT的浓度可以改变活性膜的色度、拉伸强度、含水量及膜内山梨酸钾的释放行为;使用Fickian第二定律模拟山梨酸钾释放是可靠的,可为山梨酸钾抗菌包装材料的进一步开发利用提供参考。