Modification of zein films by incorporation of poly(ethylene glycol)s

The thermal and mechanical properties of corn (maize) (CZ) films plasticized with poly(ethylene glycol) (PEG) of two different molar masses (400 and 1000 g mol⁻¹) were studied using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), tensile strength, moisture absorption isotherms and water vapour transmission rate measurements. The glass transition temperature (T_g) of plasticized films is determined primarily by the amount of moisture contained in the film. DMTA data show contraction of films with loss of absorbed water during heating/cooling cycles. The moisture absorption behaviour of films plasticized with PEG400 and PEG1000 is similar at low relative humidities but significantly different at higher relative humidities. Incorporation of up to about 30 wt% PEG substantially enhances the tensile strength and the resistance to water vapour transmission of the protein film, and PEG1000 is more effective than PEG400. © 2000 Society of Chemical Industry     

Studies on glass transition temperature of mono and bilayer protein films plasticized by glycerol and olive oil

Thermomechanical and thermal properties of whey protein, maize prolamin protein (zein), and the laminated whey protein–zein films were studied. The dynamic mechanical (thermal) analysis (DMTA) results showed that the single zein film had higher T_g than single whey protein and zein–whey laminated films. The shift in the T_g values of films from 31.2°C in whey protein film and 88.5°C in the zein film to 82.8°C in the laminated whey protein–zein films may be implied some interaction formation between the two polymers. The small tan δ peaks were observed at ?50°C in zein–glycerol films and at ?22.37°C in the whey protein films and can be related to β‐relaxation phenomena or presence of glycerol rich region in polymer matrix. Zein‐olive oil and zein–whey protein–olive oil films showed tan δ peaks corresponded the T_g values at 113.8, and 92.4°C, respectively. Thus, replacing of glycerol with olive oil in film composition increased T_g. A good correspondence was obtained when DSC results were compared with the tan δ peaks in DMTA measurements. DSC thermograms suggested that plasticizers and biopolymers remained a homogeneous material throughout the cooling and heating cycle. The results showed that T_g of zein–glycerol films predicted by Couchman and Karasz equation is very close to value obtained by DSC experiments. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

PPC/PDAP共混膜的制备和性能

将过氧化二异丙苯(DCP)置于特定温度下,引发邻苯二甲酸二烯丙酯(DAP)在聚碳酸亚丙酯(PPC)溶液中聚合,制备得到聚碳酸亚丙酯/聚邻苯二甲酸二烯丙酯(PPC/PDAP)共混膜。采用红外光谱仪(FTIR)、X射线衍射仪(XRD)、差示扫描量热仪(DSC)、热重分析仪(TGA)、万能试验机和水蒸气透过率测试仪对共混膜的红外吸收、结晶性、热、力学和阻隔性能进行了表征。结果表明,通过DAP的聚合,提高了PPC的结晶性,使PDAP在PPC基体中形成交联网络,提高了共混膜的热、力学和阻隔性能。相比纯PPC,当DAP含量为20%时,共混膜的玻璃化转变温度和拉伸强度分别提高了5.3℃和266%;当DAP含量为40%时,共混膜的失重5%热分解温度提高了50.9℃,透湿系数下降了25%,因此,阻隔性能得到了提升。     

Physicomechanical,optical, barrier,and WAXS studies of filled linear low‐density polyethylene films

Linear low‐density polyethylene (LLDPE) with different fillers such as silica, mica, and soy protein isolate were compounded using a single screw extruder and blown into films by a Konark blow‐film machine. The filled LLDPE films were characterized for physicomechanical and optical properties. Barrier properties such as water vapor transmission rate and oxygen transmission rate of the filled LLDPE films were also reported. Microcrystalline parameters such as crystal size (〈N〉) and lattice distortion (g in %) of the filled LLDPE films were estimated from the wide‐angle X‐ray scattering method using Hosemann's paracrystalline model. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2938–2944, 2003     

Food compatibility and degradation properties of pro‐oxidant‐loaded LLDPE film

To avoid environmental hazards, packaging industries are aiming to produce biodegradable films for food contact safety and its degradation. LLDPE film containing 1% pro‐oxidant additive was studied for food compatibility in different simulants, at room temperature conditions as per Bureau of Indian Standards (BIS), code of federal regulations (CFR), food and drug administration USA (USFDA), and European Economic Commission directives (EEC) specifications. Overall migration values were well within the specified limits for food contact applications at room temperature filling and storing. The pro‐oxidant loaded LLDPE film was also studied for its degradation behavior with the changes in physical and mechanical properties along with thermal behavior, morphology and infrared spectroscopy. The molecular oxidations of pro‐oxidant‐loaded LLDPE films are severed which increases hydrophilicity. Evidently, the oxidation renders the material much more vulnerable to microbial attack. The combined effect of both photo and bio degradation is most effective for complete degradation of film. The results obtained from these studies revealed that the fine balance (1%) of pro‐oxidant contents in the film guarantees food contact safety and its degradation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39756.     

Effect of starch on thermal,mechanical, and barrier properties of low density polyethylene film

Low‐density polyethylene (LDPE) with different quantities of starch was compounded using a twin screw extruder and blown into films by a Konar K, blow‐film machine. Mechanical properties, namely percent elongation, tensile, bursting, and tear strength, as well as barrier properties, such as water vapor and oxygen transmission rate, of the filled LDPE film were studied. Thermal properties of the films were studied using DSC and DMA. Master curves at reference temperature of 30°C were obtained using software linked to DMA. Incorporation of 1% starch in LDPE has marginally affected the thermal, barrier, and mechanical properties; however, that of 5% starch filled LDPE has affected the properties to a great extent. The mechanical properties, such as percent elongation, tensile, tear, bursting, and seal strength, decreased by 19.2, 33.6, 3.60, 10.8, and 22.12%, respectively. Similarly, water vapor and oxygen transmission rate increased to 32.5 and 18.3%, respectively. Other physical properties, namely migration and thermal properties, were also affected in 5% starch filled LDPE; however, the film can still be used as packaging material. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3355–3364, 2006     

Effect of gamma irradiation on the oxygen barrier properties in ethyl-vinyl acetate/ethylene-vinyl alcohol/ethyl-vinyl acetate multilayer film

The potential changes of single-use plastic materials (EVA/EVOH/EVA multilayer film in this study) used in biopharmaceutical and food-packaging industries are investigated after several gamma irradiation doses: 30, 50, 115, and 270 kGy, and for nonsterilized samples (0 kGy) from a point of view of mechanical properties, thermal properties and permeability properties. Tensile tests, differential scanning calorimetry (DSC), oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) are performed on the multilayer film. For irradiation doses below 50 kGy, thermal and water vapor barrier properties are not altered. For higher doses (50 to 270 kGy), mechanical, thermal and water vapor barrier properties are slightly altered whereas oxygen barrier property decreases from 13 to 27 cm³.m⁻².day⁻¹. This slight change is shown not to happen due to chain entanglement or chain mobility loss in the amorphous phase of the different polymers. It rather comes from a change of the chemical environment of the EVOH layer.     

Colloidal Cu nanoparticles/chitosan composite film obtained by microwave heating for food package applications

In this paper, we describe the preparation and characterization of colloidal Cu nanoparticles/chitosan composite film (composite film) by solution-casting technique with microwave heating. Effects of the incorporation of colloidal Cu nanoparticles on structure, thermal behavior, surface, barrier properties and light transmission of composite film were investigated. The antimicrobial activity of films against Staphylococcus aureus and Salmonella enterica serovar Typhimurium, were also tested. Incorporation of colloidal Cu nanoparticles on chitosan matrix improved the barrier properties of films, decreasing the oxygen permeability as well as water vapor permeability and increasing the protection against UV light. The composite film was effective in alteration of cell wall and reduction of microbial concentration in the liquid culture for both bacteria tested.     

Preparation and physical properties of LLDPE grafted with novel nonionic surfactants

Copolymers of linear low‐density polyethylene (LLDPE) grafted with two novel nonionic surfactants, acrylic glycerol monostearate ester (AGMS) and acrylic polyoxyethylenesorbitan monooleate ester (ATWEEN80), containing hydrophilic and hydrophobic groups and 1‐olefin double bond were prepared by using a plasticorder at 190°C. To evaluate the grafting degree, two different approaches based on ¹H‐NMR data were proposed, and FTIR calibration was showed to validate these methods. The rheological response of the molten polymers, determined under dynamic shear flow at small‐amplitude oscillations, indicated that crosslinking formation of the chains could be decreased with increasing the monomer concentration. Their thermal behavior was studied by DSC and polarization microscope (PLM): The crystallization temperature (T_C) of grafted LLDPE shifted to higher temperature compared with neat LLDPE because the grafted chains acted as nucleating agents. Water and glycerol were used to calculate the surface free energy of grafted LLDPE films. The results indicated that the novel polyoxyethylene surfactant ATWEEN80 could greatly improve the hydrophilicity of LLDPE and the surface free energy varied from 33 mN/m of neat LLDPE to 106 mN/m of the grafted LLDPE film. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

干燥温度对纳米氧化石墨烯/PHBH复合膜结构及性能的影响

通过溶液浇铸法制备得到纳米氧化石墨烯（GO）/聚羟基丁酸-羟基己酸酯（PHBH）复合膜,利用SEM、XRD、DSC、拉伸测试、阻隔测试及透明度测试等检测手段,研究了不同干燥温度对复合膜结构及性能的影响,优化了制备工艺。结果表明：随着干燥温度的升高,GO在PHBH中的分散性以及复合膜的结晶度、断裂伸长率和阻隔性先增加后减小,而拉伸强度及透光率则随温度的增加而增加。当干燥温度为45℃→55℃梯度升温时,GO在PHBH中均匀分散,且复合膜的断面光滑,有良好的结晶度、热稳定性、力学及阻隔性能,其拉伸强度、断裂伸长率可分别达到20.11MPa、17.47%,且透氧系数及水蒸气透过系数分别为48cm³/(m²·d)、13.33g/(cm²·d),综合性能优于其他干燥温度下的复合膜。     

Preparation and Properties of a Reactive Type Nonionic Surfactant Grafted Linear Low Density Polyethylene

Summary A reactive type nonionic surfactant, monostearic acid monomaleic acid glycerol diester (MMGD) was synthesized in our laboratory. Grafting-copolymerization of linear low density polyethylene (LLDPE) with MMGD was carried out by using β ray irradiation in air in a twin-screw extruder. Evidence of the grafting of MMGD as well as its extent was determined by Fourier-transformed infrared (FT-IR) spectroscopy. The effects of monomer concentration, reaction temperature and screw run speed on degree of grafting were studied systematically. The thermal behavior of LLDPE-g-MMGD was investigated by using differential scanning calorimety (DSC). Compared with neat LLDPE, the crystallization temperature (T_c) of LLDPE-g-MMGD increased about 3 °C, and the melting enthalpy (ΔH_m) decreased with increase of MMGD content. It showed that the grafted MMGD monomer onto LLDPE acted as a nucleating agent. The tensile properties and light transmission of blown films were determined. Comparing with neat LLDPE film, no obvious changes could be found for the tensile strength, elongation at break and right angle tearing strength of LLDPE-g-MMGD film. The wettability is expressed by the water contact angle. With an increasing percentage of MMGD, the contact angles of water on film surface of LLDPE-g-MMGD decrease monotonically. Accelerated dripping property of film samples was investigated. The dripping duration of LLDPE-g-MMGD film and commercial antifog dripping film at 60 °C were 52 days and 17 days, respectively.     

Effects of the lamination temperature on the properties of poly(ethylene terephthalate-co-isophthalate) in polyester-laminated tin-free steel can — I. Characterization of poly(ethylene terephthalate-co-isophthalate)

The effects of lamination temperature on the properties of poly(ethylene terephthalate-coisophthalate) (co-PET), such as thermal, mechanical, and barrier properties, have been investigated in co-PET laminated steel. The variation of the degree of crystallinity and the orientation of the co-PET film during the lamination process was examined using DSC, X-ray diffraction, and birefringence, and water vapor permeability was also measured with varying lamination temperature. Both the degree of crystallinity and the orientation of the co-PET film decreased and water vapor permeability increased with increasing lamination temperature. The stress-strain curves of the co-PET films were different, depending on the lamination temperature. The stress in the co-PET film laminated at higher temperature was lower at a given strain, due to the increase of the amorphous region. The effects of annealing temperature and the extent of drawing on the residual stress in co-PET/tin-free steel (TFS) joints were investigated by examining the stress relaxation behavior of co-PET. It was necessary to heat co-PET/TFS joints at more than 150°C in order to eliminate the residual stress.     

Thiol–ene networks and reactive surfaces via photoinduced polymerization of allyl ether functional hyperbranched polymers

A series of allyl ether functionalized hyperbranched (HB) polyester of three generations was synthesized from commercially available Boltorn^®. These modified HB polymers were homopolymerized to form films with a large number of residual allyl ether groups available for post film formation reactions. Additionally, the polyester multifunctional molecules were cured with a di and tetrathiol monomer in a one to one molar ratio to determine the effect of conversion on the resulting network thermal and physical properties. The same UV-cure chemistries were carried out with a similar second generation polyester dendrimer for comparison. This was in an effort to determine if there is any significant difference in the film chemical conversion and properties with dendrimers in comparison to HB molecules. The highly crosslinked films were obtained and characterized with respect to physical (DMTA) and thermal (DSC and TGA) properties.     

Oxygen barrier and enthalpy of melting of multilayer EVOH films after pressure‐assisted thermal processing and during storage

Pressure‐assisted thermal processing (PATP) is an advanced thermal process involving application of elevated pressures above 600 MPa on a preheated food for a holding time of 3 to 5 min, causing the volumetric temperature of food to increase above 100°C, to inactivate bacterial spores and enzymes. This study evaluated the influence of PATP on two state‐of‐the‐art multilayer EVOH films. Flexible pouches containing water as the food simulant were made from the two films and processed at 680 MPa for 3 min at 105°C and 680 MPa for 5 min at 100°C. Each film was investigated for its oxygen transmission rates (OTRs), melting temperature (T_m), enthalpy of melting (ΔH), and overall crystallinity before (control) and after processing. The changes in OTRs and total ΔH of the two films were also analyzed during a storage period of 240 days in ambient conditions after processing. Results showed a significant (P < 0.05) increase in the OTRs of the two films after PATP. However, PATP did not cause a significant (P > 0.05) change in the T_m and ΔH of the two films. The overall crystallinity of film A decreased, but improved slightly for film B after PATP. A recovery in the OTRs of the two films occurred during storage. The films also showed changes in the total ΔH measured during the storage period, which was used to explain the changes in the oxygen barrier properties. The OTR of both films remained below 2 cc/m² day, which is required in packaging applications for shelf‐stable foods with a 1‐year shelf life. This work demonstrates the advantages of using multilayer films containing EVOH as the barrier layer in PATP applications to produce shelf‐stable foods. This work also highlights the advantage of, DSC analysis for studying the physical ageing of polymers during storage. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fusion bonding of maleated polyethylene blends to polyamide 6

Blends of linear low-density polyethylene (LLDPE) and linear low-density polyethylene–grafted maleic anhydride (LLDPE-gMA) were used to promote the adhesion to polyamide 6 (PA) in a three-layer coextruded film without using an additional adhesive or tie layer. The effect of bonding time and molecular weight (MW) of different maleated polyethylenes on the peel strength of the joints was analyzed. Direct evidence of a copolymer formed in-situ at the interfaces is also considered. The peel strength of fusion bonded layers of LLDPE/LLDPE-gMA blends with PA strongly depends on bonding time and molecular weight of the maleated polymer. Tensile properties of three-layer films, made up of PA as the central layer and LLDPE/LLDPE-gMA blends as the two external layers, are improved with increases in the maleic anhydride (MA) content in the blend. The in-situ formation of a copolymer between the MA in the blend and the terminal amine groups of the PA was confirmed by the Molau test, infrared (IR) spectroscopy, and thermal analysis (DSC).     

Performance of multilayer films using maleated linear low-density polyethylene blends

Blends of linear low-density polyethylene (LLDPE) and linear low-density polyethylene grafted maleic anhydride (LLDPE-gMA) were prepared by melt mixing and then coextruded as external layers, with a central layer of polyamide (PA) on three-layer coextruded flat films. Blends with contents of 0% to 55 wt% of maleated LLDPE, on the external layers, were analyzed. The T-peel strength and oxygen and water vapor transmission rate of the films were measured. The surfaces of the peeled films were characterized using attenuated total reflection infrared spectroscopy (FTIR-ATR) and scanning electron microscopy (SEM). The observed increase in T-peel strength of the films with 10% and higher levels of maleated LLDPE in the blend suggests good interfacial adhesion between layers. This sharp increase in peel strength appears to be associated, besides interdiffusion, with specific interactions between polymers, as the bond formation between maleic anhydride and the polyamide end groups by in situ block copolymer formation across the interface. No significant modifications in oxygen barrier properties of the films were observed; however, the use of higher contents of LLDPEgMA, even though it increases the adhesion performance, also increases the water vapor transmission rate by a reduction in the degree of crystallinity.     

Polyethylene with MoS2 nanoparticles toward antibacterial active packaging

Molybdenum disulfide (MoS₂) nanoparticles, obtained from liquid phase exfoliation in the presence of chitosan, were melt mixed with a linear low-density polyethylene (LLDPE) matrix to produce novel antimicrobial active packaging materials. The LLDPE/MoS₂ composites presented exfoliated nanoparticles forming aggregates that are well dispersed in the polymer matrix. These 2D-layered MoS₂ nanoparticles at concentrations of 0.5, 1.0, and 3.0 wt% rendered several functionalities to the LLDPE, as for example an antimicrobial behavior against Salmonella typhi and Listeria monocytogenes bacteria that can be explained not only by the photoactivity of the filler but also by changes in the composite surface. For instance, the composites presented a reduction in the water contact angle (i.e., an increased hydrophilicity) and relevant changes in the surface topography (i.e., reduced roughness) as compared with pure LLDPE. Regarding the barrier properties, while MoS₂ dramatically increased the water vapor permeation (WVP) of the polymer matrix, until 15 times for composite with 3.0 wt% of filler, the oxygen permeation decreased around 25%. All these novel functionalities in the nanocomposites were obtained without significantly affecting the tensile mechanical properties of the pure LLDPE matrix. These results show that MoS₂ is a promising filler for the development of antibacterial active packaging films with behaviors as similar as other 2D-layered fillers such as graphene derivatives.     

Poly(propylene carbonate)/aluminum flake composite films with enhanced gas barrier properties

A series of poly(propylene carbonate) (PPC)/aluminum flake (ALF) composite films with different ALF contents were prepared via a melt‐blending method. Their cross‐section morphologies, thermal properties, tensile strength (TS), and gas barrier properties were investigated as a function of ALF contents. SEM images reveal the good dispersion and orientation of ALF along with melt flow direction within PPC matrix. The oxygen permeability coefficient (OP) and water vapor permeability coefficient (WVP) of the composite films decrease continuously with ALF contents increasing up to 5 wt %, which are 32.4% and 75.2% that of pure PPC, respectively. Furthermore, the TS and thermal properties of PPC/ALF composite film are also improved by the incorporation of ALF particles. The PPC/ALF composite films have potential applications in packaging area due to its environmental‐friendly properties, superior water vapor, and oxygen barrier characteristics. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41663.     

Effect of in situ apatite on performance of collagen fiber film for food packaging applications

This study attempted to prepare apatite in situ in acid‐swollen cowhide collagen film by an ammonia gas fumigating method and assess its reinforcement effect on a collagen fiber film for food packaging applications. The X‐ray diffraction and Fourier transform infrared spectroscopy results confirmed the successful synthesis of apatite in collagen fiber films. SEM images showed that tiny apatite particles appeared as a coating on the film surface and also made the film's inner structure more compact and less porous than pure collagen fiber film. Apatite significantly (p < 0.05) increased the tensile strength and improved the water vapor barrier and water insolubility properties of collagen fiber film. Moreover, the thermogravimetric and differential scanning calorimetry results confirmed that the thermal stability of collagen was improved with the increasing apatite. The in situ–synthesized apatite provided a practical reinforcement approach to improving the collagen fiber film's performance and benefited its application as a food packaging material. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44154.