Effect of plasticizing sugars on rheological and thermal properties of zein resins and mechanical properties of zein films

Zein is the most important protein in corn. Zein has good film forming properties. One of the film forming methods is production of zein resin and then thermomolding by hot press. Pure zein film is very brittle. Plasticizers can improve mechanical and film making properties of zein. In this research, sugars (fructose, galactose and glucose) were used as plasticizers and rheological properties of zein resin were studied by dynamic oscillatory tests for determination of plasticization effectiveness. Effect of plasticizers on thermal properties of resins was investigated by DSC at −100 to 150 °C. No crystallization and melting peaks related to zein and plasticizers were observed. As well as there was not significant difference at glass transition temperature between zein resins containing various sugars. Zein films were prepared from zein resins by rolling and hot press and then mechanical properties of films were measured. Films containing galactose had better tensile properties than other films and showed higher tensile strength, strain at break, and Young modulus than films containing fructose and glucose.     

Mechanical and Thermal Characteristics of Pea Starch Films Plasticized with Monosaccharides and Polyols

Edible starch films were produced from pea starch and various plasticizers (mannose, glucose, fructose, and glycerol and sorbitol) at the ratio of 4.34, 6.50, 8.69, and 10.87 mmol plasticizer per gram of starch. After film specimens were conditioned at 50% relative humidity, mechanical properties (tensile strength, elongation, and modulus of elasticity), water vapor permeability (WVP), moisture content, and thermomechanical properties (G’ and tan8) were determined as a function of plasticizer concentration. At all concentration levels, monosaccharides (mannose, glucose, and fructose) made the starch films stronger (higher tensile strength) and more stretchable than polyols (glycerol and sorbitol), while WVP of monosaccharide‐plasticized starch films were lower than those of polyol‐plasticized starch films, especially at higher plasticizer concentration levels. Except for 4.34 mmol/g of mannose‐plasticized film, all the other films showed similar modulus of elasticity at the same plasticizer concentration. Polyol‐plasticized films had lower T than the monosaccharide‐plasticized films. Glucose‐ and sorbitol‐plasticized films needed more activation energy to go through glass transition than others. After all, research results showed that not only the polyols but also the monosaccharides were effective in plasticizing starch films. It is concluded that molecular size, configuration, total number of functional hydroxyl group of the plasticizer as well as its compatibility of the plasticizers with the polymer could affect the interactions between the plasticizers and starch molecules, and consequently the effectiveness of plasticization.     

Alginate-calcium films: Water vapor permeability and mechanical properties as affected by plasticizer and relative humidity

Alginate films containing dissimilar amounts of guluronate (G) and mannuronate (M): M/G∼0.45 and M/G∼1.5, soaked in a calcium chloride solution up to 20 min were evaluated for water vapor permeability (WVP). M/G∼0.45 films proved to be better moisture barriers at all calcium immersion times compared to M/G∼1.5. WVP of M/G∼0.45 and M/G∼1.5 films decreased as time of immersion in calcium increased; after 3 min, a decrease in WVP was observed. M/G∼0.45 films soaked for 1 min in calcium were further analyzed to determine the effect of plasticizer and relative humidity (RH) on their mechanical properties and WVP, using fructose, glycerol, sorbitol, and polyethylene glycol (PEG-8000). Films without plasticizer showed a lower capacity to adsorb water compared to those with plasticizer. As RH increased, tensile strength (TS) decreased and elongation (E) increased for all films. This effect was more pronounced on films containing plasticizer, which had lower TS at all RHs. Plasticizer did not increase E at 58% RH. At 78% and 98% RH, glycerol, sorbitol and fructose showed a significant increase in E compared to PEG-8000 and no-plasticizer. PEG-8000 provided lower TS and E, while glycerol showed the highest among all plasticizers. There was no difference on WVP between no-plasticizer and glycerol. Fructose and sorbitol showed the lowest WVP while PEG-8000 showed the highest.     

Mechanical Properties, Water Vapor Permeabilities and Solubilities of Highly Carboxymethylated Starch-Based Edible Films

ABSTRACT: Tensile strength (TS), elongation (E), water vapor permeabilities (WVP) and solubilities were determined for highly carboxymethylated starch (HCMS)-based edible films plasticized with sorbitol (S), xylitol (X), mannitol (M) and glycerol (G). TS and E of HCMS-based film increased as the concentration of plasticizer S, M or × increased. TS of the HCMS-based film containing combined plasticizers were higher than those of films containing single plasticizer. The WVP of HCMS-based films seemed to decreased as the concentration of M, X or G plasticizer increased. Increasing plasticizer concentrations in HCMS-based film resulted in decreasing solubility of the films.     

Water vapor and oxygen-barrier performance of corn–zein coated polypropylene films

A novel corn–zein coating structure on polypropylene (PP) films was developed to examine its feasibility as an alternative water vapor and oxygen-barrier for flexible packaging industry. The barrier properties of the resulting films were evaluated as affected by coating formulation (solvent, corn–zein, plasticizer concentration and plasticizer type). Corn–zein with different amounts (5% and 15%) was dissolved in 70% and 95% aqueous ethanol solution at 50 °C, respectively. Solutions of corn–zein plasticized by polyethylene glycol (PEG) and glycerol (GLY) with various levels (20% and 50%) were applied on corona-discharged-treated PP by using solvent-casting method. The significant improvements in water vapor and oxygen-barrier properties of uncoated PP films were obtained with corn–zein coating. Water vapor permeability (WVP) of the coated films decreased significantly with increasing corn–zein concentration. The application of plasticized corn–zein coating on PP films showed nearly more than three order of reduction in oxygen permeability (OP). The high water vapor and oxygen-barriers were obtained for films coated with coating formulation consisting of higher amounts of corn–zein plasticized by GLY. The statistical analysis defined the key parameters of coating formulation that had major effect on the final properties of coated PP films as corn–zein, plasticizer concentration, and plasticizer type.     

Kefiran films plasticized with sugars and polyols: water vapor barrier and mechanical properties in relation to their microstructure analyzed by ATR/FT-IR spectroscopy

Kefiran, an exopolysaccharide produced by microorganisms present in kefir grains, is a glucogalactan that has several health promoting properties. In the present work the effect of different sugars (glucose, galactose, sucrose) and polyols (glycerol and sorbitol) as plasticizers on kefiran film properties was evaluated. Kefiran films were brittle and rigid and all the tested plasticizers improved film properties. They were all transparent with low opacity. Unplasticized kefiran films X-ray diffraction patterns were similar to those of plasticized ones, showing an amorphous-crystalline structure with low crystallinity degree. All films presented low a_w values (below 0.5) conferring protection properties against microorganism growth. The lowest permeability value was obtained with glucose as plasticizer whereas the best mechanical properties were obtained with glycerol addition.     

油酸与甘油对玉米醇溶蛋白膜机械性能的影响及机理探讨

主要研究了两种性质不同的增塑剂（油酸和甘油）对玉米醇溶蛋白（zein）膜机械性能的影响和可能的机理,以抗拉伸强度（TS）、伸长率（E）、透水率（WVP）为指标,结果发现油酸和甘油都能显著改善zein膜的机械性能,且添加量都以20%（g/g zein）最优;复合增塑研究发现,当添加20%混合增塑液对zein膜进行增塑时,以油酸∶甘油为3∶1复合增塑的效果最好,其中与未增塑的zein膜相比,TS提高190%,E提高70%。进一步统计学分析表明,油酸与甘油在对zein膜增塑时有正协同作用。对未增塑、20%油酸增塑、20%甘油增塑及20%复合增塑（油酸∶甘油为3∶1）zein膜的玻璃态转化温度（Tg）及红外光谱（FT-IR）分析发现,增塑后的zein膜Tg有所下降,其中复合增塑降幅最大;FT-IR图谱分析发现,复合增塑时甘油的特征峰向高波长方向移动,显示增塑作用加强;蛋白二级结构分析发现,复合增塑后,二级结构虽有小幅改变,但并未达到显著水平,因此增塑剂与zein之间的非共价键相互作用（疏水力和氢键）可能是其增塑的化学基础。      

Effects of various plasticizers and nanoclays on the mechanical properties of red algae film

To manufacture red algae (RA) film, we used various plasticizers such as glycerol, sorbitol, sucrose, fructose, and polypropylene glycol (PPG), and then determined the mechanical properties of the RA films. The tensile strength (TS), elongation at break (E), and water vapor permeability (WVP) of the films containing various plasticizers ranged between 0.43 to 9.10 MPa, 10.93% to 47.17%, and 1.28 to 1.42 ng m/m2sPa, respectively. RA films containing fructose as a plasticizer had the best mechanical properties of all the films evaluated. Incorporation of nanoclay (Cloisite Na+ and 30B) improved the mechanical properties of the films. RA film with 3% Cloisite Na+ had a TS of 10.89, while RA film with 30B had a TS of 10.85 MPa; these films also had better E and WVP values than the other RA films evaluated. These results suggest that RA/nanoclay composite films are suitable for use as food packaging materials. PRACTICAL APPLICATION: Edible RE/nanoclay composite films prepared in the present investigation can be applied in food packaging.     

Combined effect of plasticizers and surfactants on the physical properties of starch based edible films

Films made of potato starch were developed and glycerol as plasticizer and Tween 20, Span 80, and soy lecithin as surfactants were included in the formulation. Films were characterized with respect to water vapor permeability (WVP) and mechanical properties. The wettability of the film solutions was quantified by measuring their surface tension.The incorporation of plasticizers resulted in more flexible and manageable films and higher WVP. At low concentration, Tween 20 was the surfactant that reduced surface tension the most, while at high concentration it was lecithin. In the absence of glycerol, surfactants had a significant effect on mechanical properties, but they did not modify significantly WVP of the films. It was observed a synergistic behavior between the plasticizer and the surfactants. Films with glycerol and high level of any of the surfactants behaved as films with larger amount of plasticizer (with lower tensile strength, higher elongation, and higher WVP). Tween 20 was the surfactant that showed the most intense synergistic effect with glycerol.     

玉米醇溶蛋白膜的降解性能和水蒸气透过率的研究

对玉米醇溶蛋白（zein）与3%油酸增塑的玉米醇溶蛋白（OA-zein）膜的降解性能和水蒸气透过率进行了研究,实验结果表明：zein膜和OA-zein膜具有良好的抗酸性,但在pH 10以上时开始发生降解,蛋白酶水解实验表明了24h内蛋白膜不被酶水解.这些数据说明了蛋白膜在人体内不能被消化,但在碱性环境中可以降解.水蒸气透过率实验证明了蛋白膜所具备良好的阻气性能,可以作为疏水性的包覆材料应用于医药、食品和化工领域.     

Sorption isotherm and plasticization effect of moisture and plasticizers in pea starch film

Pea starch films were produced with various plasticizers (glucose, fructose, mannose, sorbitol, and glycerol). Effects of plasticizer content (4.34 to 10.87 mmol/g of dry starch) and storage relative humidity (RH) (11.3% to 75.4%) on moisture content (MC), tensile strength (TS), elongation (E), modulus of elasticity (EM), and water vapor permeability (WVP) were evaluated using response surface methodology. MC was influenced strongly by RH. Glycerol-plasticized films had the highest MC, indicating that water molecules played a more important role in plasticizing starch films. Monosaccharide-plasticized films and polyol-plasticized films had similar TS values. However, monosaccharide-plasticized films had higher E values and lower EM values than polyol-plasticized films, meaning monosaccharides had better efficiency in plasticizing starch films. Recrystallization happened in glucose- and sorbitol-plasticized films when they were stored in high RH. Sorption isotherm studies showed the similar adsorption and desorption profiles for all 3 monosaccharide-plasticized films and a hysteresis. The Flory-Huggius model fitted experimental data best for starch films, while the BET model fitted the data marginally.     

Mechanical and Barrier Properties of Egg Albumen Films

Films were cast and dried from heated, alkaline aqueous egg albumen solutions containing glycerin (GLY) at 30, 40, or 50% w/w of protein, polyethylene glycol (PEG) at 50 or 60%, or sorbitol (S) at 50 or 60% as plasticizers. PEG-plasticized (60%) films also were prepared by substituting 10, 30, 50, or 70% of albumen with yolk solids. Film tensile strength (TS), elongation at break (E), water vapor permeability (WVP), and Hunter color values were measured. At a plasticizer content of 50%, films with S had the lowest WVP while films with PEG had the greatest E. S- and PEG-plasticized films had greater TS than GLY-plasticized films. Yolk solids decreased film TS, E, and WVP while increasing film yellowness.     

Water Vapor Permeability and Mechanical Properties of Soy Protein Isolate Edible Films Composed of Different Plasticizer Combinations

Water barrier and mechanical properties were measured for soy protein isolate (SPI) films plasticized with glycerol (GLY) and 1 of the plasticizers (propylene glycol [PG], polyethylene glycol [PEG], sorbitol [SOR], or sucrose [SUC]) at a ratio of 25:75, 50:50, 75:25, and 0:100. Plasticizer type as well as the plasticizer ratio in the GLY: plasticizer mixtures affected the film water barrier and mechanical properties. An addition of as little as 25% of a less hygroscopic plasticizer in the mixture induced significant reduction in water vapor permeability (WVP) of SPI films. However, at least 50% of the mixture needs to be GLY to show significant improvement in tensile strength (TS). From our experimental design, 50:50 GLY:SOR was the recommended combination because of its comparatively low WVP value and relatively high flexibility and strength. Incompatibility of GLY:PEG plasticizer mixture in SPI film was observed by surface migration of PEG from the film matrix.     

Mechanical and water vapor barrier properties of extruded and heat-pressed gelatin films

Gelatin-based edible films were produced by extruding hot melt of gelatin-based resins through a die with slot orifice and followed by heat-pressed method. The resins were plasticized with glycerol, sorbitol and the mixture of glycerol and sorbitol (MGS). The effect of type of plasticizer on extruded and heat-pressed (EHP) film-forming capacity was studied, and the mechanical and water barrier properties of resulting EHP gelatin films were compared with those of gelatin films prepared by solution casting method. Stretchable films were formed when glycerol or MGS were used as plasticizer, whereas resins plasticized with sorbitol were extruded in non-stretchable sheets. Glycerol plasticized gelatin film showed the highest flexibility and transparency among the EHP films tested. Tensile strength (TS), elongation (E) and water vapor permeability (WVP) of glycerol plasticized EHP gelatin films were 17.3 MPa, 215.9% and 2.46 ng m/m² s Pa, respectively, and EHP gelatin films had higher E values, lower TS values and higher WVP values compared to the glycerol plasticized cast gelatin films.     

不同塑化剂对柠檬酸淀粉酯成膜性能的影响

以甘油、乙二醇、山梨醇和壳聚糖为塑化剂,机械活化柠檬酸淀粉酯为原料,以断裂伸长率为评价指标,通过SEM、FT-IR、TGA和接触角的分析,探讨不同塑化剂对淀粉酯成膜性能的影响。结果表明,不同塑化剂对淀粉酯的影响不同。不同塑化剂对淀粉酯膜的断裂伸长率影响为甘油>山梨醇>乙二醇>壳聚糖>原淀粉。添加塑化剂能使淀粉酯更好地成膜。SEM分析表明,以甘油和壳聚糖为塑化剂的淀粉酯膜具有更多网状结构,表面透气性好;以乙二醇和山梨醇为塑化剂的淀粉酯膜更为致密,表面相对光滑,气密性更好。FT-IR表明,淀粉酯膜均成功塑化且具有相同峰型,说明不同塑化剂的塑化机理基本相同。TGA显示,热分解温度与塑化剂分子大小及羟基含量存在密切关系。接触角分析表明,不同塑化剂对于淀粉酯膜的亲水性各不相同,其亲水性大小为山梨醇>甘油>壳聚糖>乙二醇。     

Mechanical and Barrier Properties of Lactic Acid and Rennet Precipitated Casein-Based Edible Films

Tensile strength (TS), percent elongation (%E), oxygen permeability (OP), and water vapor permeability (WVP) of lactic acid and rennet precipitated casein-based edible films were studied to determine the effect of protein to plasticizer ratio (0.6:1, 1:1, 1.4:1) and plasticizer type (sorbitol, glycerol) on these properties. TS increased (p<0.05) with increase in protein to plasticizer ratio. Sorbitol plasticized films were stronger (p<0.05) than glycerol plasticized films. However, films plasticized with glycerol were more extensible (p<0.05). Film %E decreased with increase in protein/plasticizer ratio for lactic acid casein films, whereas it increased for rennet casein films. Films plasticized with sorbitol were more effective (p<0.05) moisture and oxygen barriers than glycerol plasticized films. Overall, lactic acid casein films plasticized with sorbitol had the most effective mechanical and barrier properties.     

Effects of plasticizers on the properties of edible films from skin gelatin of bigeye snapper and brownstripe red snapper

The effects of type and concentration of plasticizers on the mechanical properties (tensile strength, TS and elongation at break, EAB), water vapor permeability, light transmission, transparency and color of fish skin gelatin edible films from bigeye snapper (Priacanthus marcracanthus) and brownstripe red snapper (Lutjanus vitta) were investigated. At the same plasticizer concentration, fish skin gelatin films from both species plasticized with glycerol (Gly) showed the greatest EAB (P<0.05), whereas ethylene glycol (EG) plasticized films showed the highest TS (P<0.05). Films prepared from brownstripe red snapper skin gelatin exhibited slightly greater TS than those of bigeye snapper skin gelatin (P<0.05) when Gly and sorbitol (Sor) were used. EG, polyethylene glycol 200 (PEG 200) and polyethylene glycol 400 (PEG 400) affected the mechanical properties of both films differently. Films generally became more transparent and EAB, water vapor permeability (WVP), as well as light transmission of films increased, but TS and yellowness decreased with increasing plasticizer concentrations.     

Stability of the physical properties of plasticized edible films from squid (Todarodes pacificus) mantle muscle during storage

Edible films from squid mantle muscle plasticized with different plasticizers were stored at 25 °C, 50% RH before the determination of physical properties. The results showed that tensile strength significantly increased (P < 0.05) upon the storage time, especially for the film plasticized with glucose, while there was no significant change (P ≥ 0.05) in elongation at break of all plasticized films. Water vapor permeability of glucose-plasticized film significantly decreased (P < 0.05) during storage, while there was only a slight change in those with glycerol, sorbitol, and fructose. Redness and yellowness of the films became significantly higher (P < 0.05) during storage, especially for the films plasticized with fructose and glucose. SDS-PAGE and protein solubility in SDS solution showed a possibility of protein aggregation throughout the storage. From these results, it is suggested that the changes in physical properties of the films were caused by the progress of Maillard reaction. PRACTICAL APPLICATION: In this study, squid mantle muscle was used as an edible film-forming material. By mixing with Na-citrate, squid mantle muscle possessed the ability to form transparent films with an excellent UV barrier property. Glycerol was found to be the most effective and stable plasticizer for the films. Edible films represent an option for the utilization of discarded squid during the fishing process.     

Influence of plasticizers on the water sorption isotherms and water vapor permeability of chicken feather keratin films

Biodegradable films from many protein sources have in recent decades attracted a lot of attention for their potential use in food protection because they have several advantages over synthetic films, including those related to the environment. The effects of type and concentration of plasticizers on microstructure, sorption isotherms and water vapor permeability (WVP) of films obtained from chicken feather keratin (CFK) were investigated. Keratins were extracted with an aqueous solutions of urea, 2-mercaptoethanol and surfactant. The protein was dosed and the maximum concentration achieved was 12 g/100 ml. The protein concentration in the keratin film solution was standardized at 7 g/100 ml for the preparation of the films by casting. The results showed that increasing the plasticizer concentration caused a decrease in barrier properties and favored water adsorption by the polymeric network, increasing the moisture content of the films. The monolayer moisture content was 8.76 times higher for films made with glycerol than films made without plasticizer and 12 times higher than films plasticized with PEG 4000. The same behavior was observed for the water solubility coefficient, which increased with increasing plasticizer concentration.     

Effects of various plasticizers on mechanical and water vapor barrier properties of gelatin films

Different kinds of plasticizers were chosen to study the effects of plasticizer composition, size and shape on the mechanical properties and water vapor permeability (WVP) of gelatin films in this paper. Firstly, oligosaccharides – sucrose, and some organic acids such as oleic acid, citric acid, tartaric acid, malic acid (MA) were added to gelatin. It was found that only MA could improve the ductility of gelatin film, and the visual appearance of MA modified gelatin film was better. Secondly, polyethylene glycols (PEG) with different molecular weights (300, 400, 600, 800, 1500, 4000, 10?000, 20?000) were used to plasticize gelatin films. This showed that PEG of lower molecular weights exhibited better plasticizing effect for gelatin films, and such films had better visual properties. This shows that mannitol (Man) and sorbitol (Sor) could make gelatin films flexible, whereas Man could crystallize from gelatin film. Following this, the plasticization of ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG) series and ethanolamine (EA), diethanolamine (DEA), triethanolamine (TEA) series was studied. At last, suitable plasticizers (MA, PEG300, sorbitol, EG, DEG, TEG, EA, DEA, TEA) for gelatin were selected to investigate the WVP and water content of these plasticized gelatin films. The mechanical properties of these films were also compared.