预测相融共混膜氧气透过率的分形渝渗模型

目的 预测相融体系共混膜氧气透过率,为高阻氧共混膜的生产和设计提供理论依据.方法 应用分形与渝渗理论提出一种氧气透过率预测模型,该模型能够在高阻氧材料体积分数条件下更准确地估算相融体系共混膜的氧气透过率.以聚酯/聚萘二甲酸乙二醇酯(PET/PEN)共混膜为例,通过扫描电镜分析共混膜微观形貌,确定PET/PEN共混膜中氧气渗透维数,并根据渗透维数结合文中提出的预测模型计算PET/PEN共混膜氧气透过率,最后通过实验数据验证该模型的有效性.结果 氧气在PET/PEN混合膜中的渗透可以简化为二维渗透.在低PEN体积分数条件下,现有模型和文中提出的预测模型均与实验结果高度吻合.该模型在高PEN体积分数条件下展现出了现有其他模型所没有的曲线趋势,能够更准确地描述高阻氧材料在共混膜体系中对氧气的阻隔作用.结论 文中提出的预测模型能够用于预测相融体系共混膜的氧气透过率.     

Synthesis,Characterization and O2 Permeability of Shape Memory Polyurethane Films for Fresh Produce Packaging

The aim of this work was to investigate the effect of film formulations in an effort to obtain a fresh produce packaging film with increased temperature sensitivity for gas permeability. Series of shape‐memory polyurethane (SMPU) were synthesized using poly(ethylene glycol) (PEG), 1,6‐hexamethylene diisocyanate, 1,4‐butanediol and castor oil (CO) and casted into films. The changes in thermal, viscoelastic, shape‐memory properties and oxygen permeability of the films were studied. The polyurethane films with 1500 g mol^?1 PEG showed a phase transition temperature (switching temperature) between 20 and 27°C. The SMPU consisting of 50/50 CO/PEG had a log E′ value of 8.32 Pa and showed good elasticity as low density polyethylene. SMPU prepared from 1500 g mol^?1 PEG with 50/50 CO/PEG and 40/60 butanediol/(PEG + CO) ratios showed excellent shape‐memory properties with shape recovery ratio >85% and shape fixity ratio >90%. This film had higher oxygen permeability and showed up to 67% increase in Q₁₀ value for oxygen permeability compared with commercial packaging films like low density polyethylene. This film can be used to develop smart packaging with increased thermally responsive gas permeability to similar levels observed in respiration rates of fresh produce. Copyright © 2016 John Wiley & Sons, Ltd.     

The transport mechanisms of gases through metallized films intended for food packaging applications

Metallized polymeric films are amongst the most favoured candidates for replacing aluminum foil‐based multilayer films. The main advantages in using the former instead of the latter are: weight saving of about 40%; much less aluminum (320 time less in weight); improved recyclability; and the possibility of optimizing package barrier properties. It is generally assumed that metallization decreases the permeability of the polymeric substrate by reducing the total area available for permeation, even though the validity of such a hypothesis has never been proved experimentally. In the present paper an attempt has been made to elucidate the role of metal coating in reducing the permeation flux of polyolefine films. For this purpose, permeability tests were performed using oxygen, nitrogen and carbon dioxide at temperatures of 20–40°C. Permeation tests have been performed on two different metallized films, on their substrates alone and on two laminates. From the analysis of the experimental results, it has been concluded that, contrary to what generally thought, gas molecules can permeate through the metallized films investigated due to both the permeable porous structure of the deposited aluminum layer and the presence of pin‐holes uniformly dispersed on the metallized film surface. Copyright © 1999 John Wiley & Sons, Ltd.     

Development of a system for measurement of permeability of aroma compounds through multilayer polymer films by coupling dynamic vapour sorption with purge‐and‐trap/fast gas chromatography

A system for measurement of permeability of aroma compounds through laminated polymer films was constructed by combining dynamic vapour sorption (DVS) with purge‐and‐trap/fast gas chromatography (P&T–fGC). Data validation was achieved by measuring the permeability of limonene across an HDPE film (film C) and comparing the permeation data with the literature values. The general applicability of this system, as well as its potential for simultaneous measurement of permeability of multiple aroma compounds, was demonstrated by measuring the permeability of limonene and ethyl butyrate as single permeants or as co‐permeants under different environmental conditions (at 25°C, 30°C or 35°C and 0% or 75% RH) through three different multilayer polymer films (film A, HDPE/EVOH/HDPE/HDPE; film B, HDPE/nylon/HDPE/HDPE; film C, HDPE/HDPE). The results showed that the aroma barrier performance of plastic films was determined by the polymer composition and was affected by various factors, such as temperature and the presence of other co‐permeants. Simplicity, speed and accuracy were some of the attractive features of this system, which indicates its potential as a useful tool that could be applied in the food industry for screening or selection of appropriate packaging materials for specific applications. Copyright © 2004 John Wiley & Sons, Ltd.     

Development of multilayer films with improved aroma barrier properties for durian packaging application

The symmetrical A/B/A structure of multilayer blown films was fabricated in this study. The immiscible low‐density polyethylene/polylactic acid (LDPE/PLA) blend was set as a core (B) layer and LDPE was used as skin (A) layers. The compositions of PLA in the core layer were varied from 20 to 50 wt%. The thickness of each layer was 10 μm (total film thickness of ~ 30 μm). In a blown film co‐extrusion process, the morphology of the fiber/ribbon‐like structures of LDPE/PLA blend was developed. Such structures had interesting effects on gas permeability and aroma barrier properties of the films. For instance, multilayer LDPE films containing 40 and 50 wt% PLA (P40 and P50) showed the reduction of oxygen permeability (PO₂) approximately 20% and 43%, respectively, compared with the neat LDPE film. A long tortuous path for gas and aroma transportation through film thickness was created from the developed ribbon‐like structures of the PLA minor phase. For durian packaging application, fresh‐cut durian of 300 g was packed in the developed multilayer films, LDPE, and HDPE (Control), stored at 4°C for 7 days. Results demonstrated that the steady‐state condition of 10% to 13% O₂ and 8% to 10% CO₂ was achieved in all packages except in the HDPE. Moreover, the P40 and P50 films exhibited an outstanding aroma barrier property for three major durian volatiles : diethyl sulfide, ethyl propanoate, and 2‐ethyl‐1‐hexanol. Overall results clearly indicated that the multilayer LDPE films containing PLA exhibited a significantly improved aroma barrier performance with optimum gas permeability desirable for modified atmosphere packaging to retain quality of fresh‐cut durian throughout the storage period.     

聚乳酸热收缩薄膜的制备与拉伸回复性能研究

目的 研究2种环保型改性剂碳酸丙烯酯(PC)和聚碳酸亚丙酯二醇(PPC)对聚乳酸(PLA)的增塑效果,以及PLA/PC、PLA/PPC这2种热收缩薄膜在拉伸回复过程中的热收缩性能、结晶性能和透氧性能。方法 采用双螺杆挤出机将PC、PPC分别与PLA共混改性,采用差示扫描量热仪(DSC)、傅里叶变换衰减全反射红外光谱(ATR–FTIR)、X射线衍射仪(XRD)、电子万能试验机、压差法气体渗透仪研究PC、PPC分别对PLA的改性效果,以及PLA/PC、PLA/PPC 2种热收缩薄膜在拉伸回复过程中的热收缩性能、结晶性能和透氧性能。结果 PC改性后的热收缩薄膜拉伸强度降低至16.8 MPa,断裂伸长率提高至26.6%,氧气透过率(To)可以达到1 020.4 cm3/(m²·d·Pa),而回复率(R_r)仅有27.5%。PPC改性后的热收缩薄膜拉伸强度降低至23.6MPa,断裂伸长率提高至12.5%,且PLA/PPC热收缩膜的R_r可以达到83.3%;在拉伸后T_o仅为915.8 cm³/...     

Foam films as thin liquid gas separation membranes

In this letter, we testify the feasibility of using freestanding foam films as a thin liquid gas separation membrane. Diminishing bubble method was used as a tool to measure the permeability of pure gases like argon, nitrogen, and oxygen in addition to atmospheric air. All components of the foam film including the nature of the tail (fluorocarbon vs hydrocarbon), charge on the headgroup (anionic, cationic, and nonionic) and the thickness of the water core (Newton black film vs Common black film) were systematically varied to understand the permeation phenomena of pure gases. Overall results indicate that the permeability values for different gases are in accordance with magnitude of their molecular diameter. A smaller gaseous molecule permeates faster than the larger ones, indicating a new realm of application for foam films as size selective separation membranes.     

Microstructural and Interfacial Designs of Oxygen‐Permeable Membranes for Oxygen Separation and Reaction–Separation Coupling

Mixed ionic–electronic conducting oxygen‐permeable membranes can rapidly separate oxygen from air with 100% selectivity and low energy consumption. Combining reaction and separation in an oxygen‐permeable membrane reactor significantly simplifies the technological scheme and reduces the process energy consumption. Recently, materials design and mechanism investigations have provided insight into the microstructural and interfacial effects. The microstructures of the membrane surfaces and bulk are closely related to the interfacial oxygen exchange kinetics and bulk diffusion kinetics. Therefore, the permeability and stability of oxygen‐permeable membranes with a single‐phase structure and a dual‐phase structure can be adjusted through their microstructural and interfacial designs. Here, recent advances in the development of oxygen permeation models that provide a deep understanding of the microstructural and interfacial effects, and strategies to simultaneously improve the permeability and stability through microstructural and interfacial design are discussed in detail. Then, based on the developed high‐performance membranes, highly effective membrane reactors for process intensification and new technology developments are highlighted. The new membrane reactors will trigger innovations in natural gas conversion, ammonia synthesis, and hydrogen‐related clean energy technologies. Future opportunities and challenges in the development of oxygen‐permeable membranes for oxygen separation and reaction–separation coupling are also explored.     

Properties of Transglutaminase Crosslinked Whey Protein Isolate Coatings and Cast Films

Whey protein is an excellent barrier material, potentially providing the low oxygen permeability and water vapour transmission rate required for packaging materials for sensitive foods. A topical issue is how to reduce the permeability of the whey protein‐based layers. One possible strategy is to apply crosslinking agents. In the present study, the enzyme transglutaminase (TG) was used for this purpose, and the following properties have been measured: oxygen permeability, water vapour transmission rate, effective water vapour diffusion, sorption and permeation coefficients, swellability, light transmission and surface energy. The use of TG was found to reduce the oxygen permeability, reduce the water vapour transmission rate and reduce the effective water vapour diffusion coefficient of the whey protein layers. This study also showed that it was possible to use sorption experiments to approximate the water vapour transmission rates. This work is novel because it deals with the packaging‐related properties of whey films crosslinked with TG. Previous studies have focused on the influence of TG on protein formulations or on the measurement of film properties, which is of little relevance for packaging applications. Copyright © 2014 John Wiley & Sons, Ltd.     

Oxygen permeation in PET bottles with passive and active walls

The aim of this paper is to provide a framework, whereby gas permeation rates through plastic packaging walls, and hence, food shelf life may be estimated. Although the approach is quite general, specific attention is given to the case of liquid‐filled polyethylene terephthalate (PET) bottles with oxygen as the permeating gas. Two situations are considered: when the walls simply provide a passive resistance to the flux (as is the case for standard PET or PET blended with some other low permeability material) and when an active gas scavenger is incorporated within the boundary material. For the passive wall, permeability data relative to oxygen have been collected from literature sources and also measured using specific oxygen transmission rate experiments. For the active walls, scavenger kinetic constants were estimated from data obtained using test bottles prepared with varying scavenger concentrations. Numerical predictions in both cases have been verified by comparison with data on gas concentration in water‐filled bottles maintained under controlled conditions for periods of up to 6 months. Copyright © 2008 John Wiley & Sons, Ltd.     

Simplified Approach Based on Polynomial Equations to Predict the Permeability of Micro‐perforated Polymeric Films

A simplified approach to predict the mass transport properties of micro‐perforated films was presented in this work. In particular, the proposed mathematical model was based on a second‐degree polynomial function. Different types of micro‐perforated films with two thicknesses (35 and 25 µm) were tested for gas and water vapour permeability, under proper conditions. The films differed in both number of holes per unit area and hole diameter. Corresponding non‐perforated films were also tested. The experimental data obtained were used to validate the model. Moreover, the surface response plot of the interactions between hole diameter and number of holes per area relative to oxygen, water vapour and carbon dioxide permeability were determined. Results of the mean relative deviation modulus (E%) between the experimental and predicted data confirmed the ability of the proposed model to predict the permeability of micro‐perforated films. Copyright © 2016 John Wiley & Sons, Ltd.     

Comparison of New Dynamic Accumulation Method for Measuring Oxygen Transmission Rate of Packaging against the Steady‐State Method Described by ASTM D3985

A new dynamic accumulation method for measuring the oxygen transmission rate (OTR) of packages and packaging films using robust and inexpensive fluorescence oxygen sensing technology has been developed. The method allows for oxygen to transfer through a given area of packaging or sample film and accumulate over time. The test volume incorporates a fluorescence‐based oxygen sensor that does not consume oxygen and therefore does not interfere with the real‐time measurement of oxygen concentration. The new method was tested against a widely used, commercially available instrument (Mocon Oxtran 2/20; Mocon, Inc., Minneapolis, MN, USA) designed around the steady‐state gas permeation measurement approach described by ASTM D3985. Sample films were chosen to provide comparison over several orders of magnitude of OTR. Specifically, sample films with OTR values in the range of 10¹, 10³ and 10⁴ ml O₂/m²/day were measured, and results using the two methods were compared. Results showed that the new dynamic accumulation method provides comparable results with the steady‐state method (ASTM D3985). Copyright © 2012 John Wiley & Sons, Ltd.     

PBAT/ZSM-5分子筛共混薄膜的制备与性能

目的 以聚己二酸-对苯二甲酸丁二酯(PBAT)为基材,制备PBAT/ZSM-5分子筛共混薄膜,研究分子筛含量对薄膜性能的影响.方法 通过共混熔融挤出流延法制得含不同质量分数ZSM-5分子筛(0％,1％,3％,5％,7％)的PBAT薄膜,测定分析不同分子筛质量分数对薄膜的颜色、透明性、结构、气体阻隔性、力学性能等性能的影响.结果 随着分子筛质量分数的增加,透明性和断裂伸长率显著降低,抗拉强度先增加后降低,质量分数为1％分子筛的薄膜抗拉强度相对较大,较纯PBAT薄膜增加了12.34％;薄膜氧气透过性能整体上呈上升趋势,二氧化碳透过性和CO2/O2透过比均逐渐增加,水蒸气透过性显著降低,与纯PBAT薄膜相比,质量分数为7％分子筛PBAT薄膜的氧气和二氧化碳透过系数分别增加了18.48％,33.51％,水蒸气透过系数下降了43.28％,CO2/O2透过比由原来的8.84增加到9.96;薄膜表面和横截断面均变得粗糙,局部区域有团聚现象,且随分子筛含量的增加而变得明显.结论 ZSM-5分子筛的少量加入,可以影响PBAT薄膜力学性能,降低其水蒸气透过性,调节薄膜的气体选择透过性,为其应用于生鲜果蔬包装提供基础.     

A Review of Thermoplastic Composites Vapour Permeability Models: Applicability for Barrier Dispersion Coatings

One of the purposes of thermoplastic composites films and barrier dispersion coatings is to minimize the permeation of gases. In both cases, fillers and other additives are added during the film preparation to improve barrier properties. A high level of understanding has resulted from the study of the interaction between filler and polymer phases of thermoplastic composites, and a number of models have been developed to predict the relative permeability of these materials. However, barrier dispersion coatings have not been modelled in this way. The aim of this review was to discuss similarities and differences of thermoplastic composites and barrier dispersion coatings that may influence the applicability of the models for barrier dispersion coatings applied to paper‐based materials. The models were developed as a function of the amount of fillers added in thermoplastic composites films and geometrical characteristics of the fillers such as size, thickness, shape and the distribution of fillers in the film. Two‐ and three‐dimensional models with oriented and random arrangement of fillers were presented. Due to the parallel orientation and the similar length and width of fillers used in barrier dispersion coatings, three‐dimensional models were more suitable to predict relative permeability. These models assumed plate‐ or circular‐shaped fillers with parallel orientation. In order to prove the models, experimental information was required. Very limited data for barrier dispersion coatings with varying the amount of fillers have been reported in the literature. For this reason, further experiments are required under varied combinations of aspect ratio and the volume fraction of fillers. Copyright © 2015 John Wiley & Sons, Ltd.     

Effects of glycerol and sorbitol on optical,mechanical, and gas barrier properties of potato peel‐based films

Potato peel is a by‐product of potato‐based food production and seen as a zero‐ or negative‐value waste of which millions of tons are produced every year. Previous studies showed that potato peel is a potential material for film development when plasticized with 10% to 50% glycerol (w/w potato peel). To further investigate potato peel as a film‐forming material, potato peel‐based films containing the plasticizer sorbitol were prepared and investigated on their physicochemical properties in addition to films containing glycerol. Due to sufficient producibility and handling of casted films in preliminary trials, potato peel‐based films containing 50%, 60%, or 70% glycerol (w/w potato peel) and films containing 90%, 100%, or 110% sorbitol (w/w potato peel) were prepared in this study. Generally, with increasing plasticizer concentration, water vapor and oxygen permeability of the films increased. Films containing glycerol showed higher water vapor and oxygen permeabilities than films containing sorbitol. Young's modulus, tensile strength, and elongation at break decreased with increasing sorbitol concentration, whereas no significant effect of plasticizer content on elongation at break was shown in films containing glycerol. Due to crystallization of films containing sorbitol as a plasticizer, potato peel‐based films containing 50% glycerol (w/w) were identified as the most promising films, characterized by a water vapor transmission rate of 268 g 100 μm m^?2 d^?1 and an oxygen permeability of 4 cm³ 100 μm m^?2 d^?1 bar^?1. Therefore, potato peel‐based cast films in this study showed comparable tensile properties with those of potato starch‐based films, comparable water vapor barrier with those of whey protein‐based films, and comparable oxygen barrier with those of polyamide films.     

Porous Ultrahigh Gas‐Permeable Polypropylene Film and Application in Controlling In‐pack Atmosphere for Asparagus

Porous polypropylene (PP) films with greater gas permeability and lower permeability ratios (β) than existing commercial films were developed for fresh produce packaging. PP containing high content of beta‐form crystal was biaxially stretched under controlled conditions. Resulting porous films with uniquely high oxygen transmission rate (OTR) of 2 659 000 cm³?m^?2?d^?1, water vapor transmission rate of 67 g?m^?2?d^?1, and β value of 0.76 was used as a “breathable window” attached to the less permeable commercial BOPP (biaxially oriented PP) lidding film. Various sizes/areas of the breathable windows were designed and tested on packaging asparagus of 400 g, at 5°C. Results demonstrated that in‐pack O₂ and CO₂ concentrations could be practically controlled and modified by changing areas of the breathable windows. Altered porous high OTR area directly affected total gas permeation of the package. Optimum gas composition of Ο₂ and CΟ₂ within the recommended controlled atmosphere for asparagus, stored at 5°C, was effectively created and maintained in the package containing 25 cm² breathable window (15% of total film lid's area). The shelf life of asparagus under optimum modified atmosphere was extended to 29 days, as compared with <3 days in the normal, low OTR tray sealed with BOPP lidding film. Clearly, these developed porous ultrahigh permeable PP films can be useful materials in designing high OTR package with desirable in‐pack O₂ and CO₂ concentrations. Copyright © 2013 John Wiley & Sons, Ltd.     

Aufgedampfte SiOx Barriereschichten unter monoaxialem Stress

SiO_x barrier layers under uniaxial stress For the study of the impact of defined mechanical uniaxial load on the gas barrier effect of a PET (Polyethylenterephthalate) film coated with silicon oxide SiO_x a measurement device was designed. The developed system is modular and can be combined to measure both water vapour and oxygen transmission rate. The gas permeation was measured after a given strain and after unloading the strain on relaxed films.The results show that strain above 1 % can be critical for the increase of gas permeation of coated films under constant stress and 4 % for relaxed film.     

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.     

打坑BOPP薄膜的透湿性能研究

打坑薄膜通过对薄膜进行打坑微处理,可提高其透氧性能及透湿性能。打坑BOPP薄膜在食品包装中得到了广泛的应用,但使用过程中其透湿性不好的问题较为突出,包装内易出现结露问题。以透湿性能为试验指标,选用2种不同透氧系数的打坑BOPP薄膜和未打坑BOPP薄膜进行了对比试验。结果表明,透氧系数大的打坑BOPP薄膜的透湿量也相对较大;同时,透氧系数相同的打坑BOPP薄膜的反面透湿量要大于其正面透湿量;对于不同透氧系数规格的薄膜,反面的透湿性增加量要大于正面的。可见,在实际应用中,不仅需要根据透氧系数来选择合适的包装用BOPP薄膜,且在应用时还需调整薄膜正反面的选择。     

PBAT/PCL共混薄膜在草莓保鲜包装中的应用

目的通过聚己内酯(PCL)来改善聚己二酸-对苯二甲酸丁二酯(PBAT)的自粘性、成膜性及气体透过性,探究不同厚度和不同气体透过性的PBAT/PCL共混薄膜包装对新鲜草莓的保鲜效果。方法利用双螺杆挤出流延机组制备不同厚度和不同气体透过性的PBAT/PCL共混薄膜,并用于草莓的密闭包装。结果纯PBAT的自粘性由于PCL的添加得到改善,且不同厚度及共混比例的PBAT/PCL共混薄膜气体透过量不同,但CO_2/O_2选择透过比几乎不变。当薄膜用于草莓包装时,PBAT/PCL20薄膜草莓包装内部的CO_2浓度从第2天开始迅速进入平衡状态,维持在体积分数为2%~3%的范围,而O_2的体积分数随着贮藏时间逐渐降低后达到6%~7%。结论少量PCL的添加可改善PBAT的自粘性,一定厚度和透过性的PBAT/PCL共混膜可以使包装内部建立起低氧高二氧化碳的气氛环境,抑制草莓的呼吸作用,延长其保鲜期。