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.     

Plasticization of Pea Starch Films with Monosaccharides and Polyols

ABSTRACT:  Monosaccharides have several hydroxyl groups and a compatible structure with starch polymers resulting in effective plasticization in starch films. Two groups of plasticizers (polyols and monosaccharides) were used to compare their plasticizing efficiency. Fructose, glucose, mannose, galactose, glycerol, sorbitol, ethylene glycol, and maltitol were selected at 13.031 mmol per 100 g of pea starch. Edible starch films were produced after heat gelatinization and dehydration of the 3% starch dispersion. The microstructure, attenuated total reflection foorier transform infrared (ATR-FTIR) characteristics, thickness, moisture content, tensile strength, modulus of elasticity, elongation-at-break, water vapor permeability, and transparency of films were determined. Microstructure of the film solutions showed that some swollen starch granules and their remnants existed in the film. Compared to the FTIR spectra of pure starch films, the spectra of plasticized films showed that more hydrogens bound hydroxyl groups and more water molecules were attracted around starch polymer chains. Ethers were produced in glycerol-plasticized films. Monosaccharide-plasticized films were comparable to the polyol-plasticized films in tensile test, but more resistant in moisture permeation than the polyol-plasticized films. It was assumed that the structural compatibility of monosaccharides with starch might result in denser polymer-plasticizer complex, smaller size of free volume, and less segmental motions of starch chains. In conclusion, monosaccharides were identified as effective plasticizers for starch film.     

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.     

增塑剂对高直链淀粉基生物降解薄膜力学性能的影响

以高直链玉米淀粉为原料,利用微波辐射加热工艺将淀粉糊化,通过溶液浇铸法制备淀粉基薄膜。探讨了不同增塑剂以及复合增塑剂对高直链淀粉基薄膜性能的影响。结果表明,甘油、山梨醇和木糖等增塑剂对淀粉的塑化作用是比较显著的。与单一的增塑剂相比,复合增塑剂所制备的材料的力学性能更加优良,尤其是甘油与木糖复合增塑所制备的淀粉基薄膜性能更好。     

Effect of Plasticizers on Mechanical and Barrier Properties of Rice Starch Film

The effect of plasticizers, glycerol, sorbitol and poly(ethylene glycol) 400 (PEG 400), on mechanical and barrier properties of rice starch film has been investigated. Sorbitol‐ and glycerol‐plasticized starch films appeared homogeneous, clear, smooth, and contained less insoluble particles compared to unplasticized rice starch films. PEG 400 did not form plasticized films of suitable characteristics. The softness and stickiness of films improved with increasing concentrations of glycerol and sorbitol. In general, films plasticized with glycerol and sorbitol displayed a better solubility in water than unplasticized films, i.e. 35% (w/w) glycerol and 45% w/w (sorbitol) (optimum solubility). The tensile strength of films decreased especially in the high concentration regime of plasticizers, between 20–45% (w/w) of plasticizer/rice starch film. Through the entire concentration regime, the tensile strength of glycerol‐plasticized films was significantly lower than that of sorbitol‐plasticized films, but their elongation was larger. The water vapor transmission rate (WVTR) through plasticized films and the oxygen transmission rate (OTR) increased with glycerol and sorbitol concentrations, however, glycerol was revealed to be significantly more effective in reducing the tensile strength as well as increasing the WVTR and the OTR compared to sorbitol. With the higher tensile strength and the smaller OTR and WVTR, the 30% sorbitol‐plasticized film reveals an improved coating performance in terms of a reduction of coating failures.     

Crystallization of High-Amylose Starch by the Addition of Plasticizers at Low and Intermediate Concentrations

ABSTRACT:  The antiplasticization effect of plasticizers (that is, polyols and monosaccharides) in starch films was investigated. Pea starch films were plasticized by various polyols and monosaccharides at the levels of 0% to 25% (w/w, plasticizer/starch). After 14 d of storage at 50% relative humidity, the crystallinity of pea starch films increased with increasing concentration of plasticizers from 0% to 20%. Accordingly, moisture content, water vapor permeability, oxygen permeability, and elongation decreased with increasing plasticizer concentration from 0% to 20%, showing the antiplasticization effect. The addition of plasticizers above 20% reduced the crystallinity of starch films, consequently showing the plasticization effect. The results showed that the addition of the plasticizers facilitated the crystallization of the polymer chains through the antiplasticization phenomenon at the concentration range below 15%. Above 20%, plasticizers performed the conventional plasticization effect. Each plasticizer had different critical concentration where the antiplasticization was converted to plasticization.     

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.     

Starch-Polyvinyl Alcohol Films –Effect of Various Plasticizers

Various polyols were evaluated as plasticizers for starch-polyvinyl alcohol films. Glycol glycoside, an experimental polyol made from starch and ethylene glycol, and sorbitol were highly effective plasticizers alone and in combination with small amounts of glycerol. Glycol glycoside is an especially attractive plasticizer because of its low production cost. Glucose and sucrose performed well in combination with glycerol or sorbitol.     

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.     

Edible films made from blends of manioc starch and gelatin – Influence of different types of plasticizer and different levels of macromolecules on their properties

The interest in the development of edible and biodegradable films has increased because it is every day more evident that non-degradable materials are doing much damage to the environment. In this research, bioplastics were based on blends of manioc starch (native and modified) and gelatin in different proportions, added of glycerol or sorbitol, which were used as plasticizers. The objective was to study the effect of two different plasticizers, glycerol and sorbitol, and different concentrations of starch and gelatin on the barrier (water vapor permeability – WVP), mechanical (tensile strength and elongation at break), physicochemical (solubility in water and in acid) and physical properties (opacity and thickness) of the obtained bioplastics samples. As a result, all of them showed transparency and resistance to tensile strength, as well as increasing in thickness values and in the WVP, as the gelatin content increased in the formulations. Finally, all results for tensile strength and elongation at break obtained for those samples plasticized with sorbitol were better than those plasticized with glycerol.     

Effect of plasticizing sugars on water vapor permeability, surface energy and microstructure properties of zein films

Sugars are natural plasticizers for food biopolymers and zein is the most important protein of corn. In this research, sugars (fructose, galactose and glucose) were used as plasticizers and the water vapor permeability (WVP), contact angle and microstructure of the zein films were studied. The pure zein film had high WVP and adding of sugars to 0.7 g/g zein caused to decrease of WVP. Films containing galactose had the lowest WVP.All samples had the lowest contact angle with ethanol and the highest contact angle with water. The zein films containing galactose had the highest water contact angle within the plasticized films. The pure zein films and the films containing fructose had higher critical surface tension of wetting (γ_c) than the films containing glucose and galactose. Adding sugar plasticizer to zein films increased the surface tension of zein films. In the unplasticized zein films, loose structures with a lot of cavities and voids were observed. The films plasticized by fructose had smooth surface and plasticizer particles distributed throughout of the films.     

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.     

Comparative study of film forming behaviour of low and high amylose starches using glycerol and xylitol as plasticizers

In this study, the film forming behaviour of low amylose (LA) and high amylose (HA) starches was studied. The starch-alone and a blend of plasticizer (polyol)-starch films were developed by gelatinising at various temperatures and casting at 25 °C. The starch-plasticizer films contained glycerol and xylitol either individually or in 1:1 combination. The concentration of plasticizer used was 15%, 20% and 30% for LA films while it was 20%, 30% and 40% for HA films on dry solid basis. The HA-glycerol films retained the highest moisture content among all the films. The HA films exhibited higher glass transition temperature, higher tensile strength, higher modulus of elasticity and lower elongation at break than those obtained from LA starch. The tensile strength and modulus of elasticity decreased and the elongation increased with increasing plasticizer concentrations above 15% on dry solid basis regardless the starch type. Low water vapour permeability was evident in LA and HA films plasticized by combined plasticizers at 20% plasticizer concentration. Rheological measurements showed that most of the suspensions exhibited Herschel-Bulkley behaviour and some of the HA suspensions exhibited Bingham plastic behaviour. At 15% (on dry solid basis) plasticizer concentration, the films obtained from both the starches were brittle due to the anti-plasticization behaviour.     

Plasticized Whey Protein Edible Films: Water Vapor Permeability Properties

Heat treatment, protein concentration, and pH effects on water vapor permeability (WVP) of plasticized whey protein films were examined. The best film formation conditions were neutral pH, aqueous 10% (w/w) protein solutions heated for 30 min at 90°. Isoelectric point adjustment of whey protein with calcium ascorbate buffer increased WVP with increasing buffer concentration, The importance of vacuum application to minimize film pore size was identified using scanning electron microscopy. Polyethylene glycol, glycerol and sorbitol plasticizer concentration affected film WVP. Determining the effects of relative humidity on WVP for plasticized whey protein films enabled prediction of film behavior under any water vapor partial pressure gradient.     

Effect of banana and plasticizer types on mechanical,water barrier,and heat sealability of plasticized banana‐based films

Unripe banana flour and starch were used to formulate plasticized banana‐based films (flour film, PBF; starch film, PBS) with two types of plasticizers (glycerol, Gly; sorbitol, Sor) and a mixture of Gly‐Sor on film properties. PBS showed greater water barrier, elongation at break, toughness, and transparency, but lower efficiency in heat sealability than PBF. However, the easier and a higher yield in the preparation process of PBF lead to higher UV and visible light barrier than PBS which could be due to its protein content and the presence of phenolic compounds in PBF. Both banana films plasticized with Sor showed high glossiness, high efficiency in heat sealability, and mechanical and water barrier properties; however, the undesirable recrystallization of white crystals resulted in lower film flexibility. Thus, Gly‐Sor was preferred without change of water barrier but strengthened heat sealability. Therefore, banana‐based film might be considered as a green food packaging material.

Practical applications

Banana flour and starch from unripe bananas can be used as safe food ingredients for food products and as green biodegradable packaging materials. Banana flour film showed similar mechanical properties as banana starch film but involved easier processing and higher yield in the preparation of banana flour. Moreover, banana flour films had higher efficiency in heat sealability with the potential to protect the packed food from UV–visible light deterioration. Furthermore, an easier way to modify proper film properties is by the proper selection of the plasticizer. A mixture of plasticizers (glycerol and sorbitol) showed high potential to improve long‐term physical stability such as through UV–visible light prevention, and improved mechanical properties and heat sealability of plasticized banana‐based films. Briefly, plasticized banana flour film with a mixture of plasticizer will be potential, alternative biodegradable packaging material to reduce the use of nonbiodegradable synthetic plastic materials in food applications.     

Effects of plasticizers, pH and heating of film-forming solution on the properties of pea protein isolate films

Effects of glycerol (3-7% w/w) and sorbitol (4-8% w/w) concentration, pH (7.0, 9.0, 11.0) and heating (90 °C, 20 min) of film-forming solution (FFS) on the water vapor permeability (WVP), moisture content (MC), solubility, light transmission and transparency of pea protein isolate (PPI) films were investigated. Films plasticized with sorbitol exhibited significantly lower WVP, lower MC and higher solubility, in comparison with glycerol-plasticized films. Increasing glycerol content of the films led to increases in WVP and MC but did not affect film solubility. In contrast, increase in sorbitol content had no effect on permeability and MC but resulted in increased film solubility. Moisture sorption isotherms of PPI films suggested that the difference in WVP observed among films plasticized with glycerol and sorbitol might be due to the different hygroscopicity of these plasticizers. The pH of FFS did not have a significant effect on WVP and MC. Solubility of PPI films formed from non-heated FFS was not affected by pH, whereas solubility of films formed from heat-treated FFS generally increased when pH was increased from 7.0 to 11.0. Heating of FFS resulted in improved film transparency. All tested films were characterized by excellent ability to absorb UV radiation. Microstructural observation by scanning electron microscopy did not show differences between sorbitol- and glycerol-plasticized films.     

Effects of Extrusion Temperature and Plasticizers on the Physical and Functional Properties of Starch Films

Cornstarch, at 20% moisture content (dry basis, d.b.), was mixed with glycerol at 3:1 ratio to form the base material for extruded starch films. Stearic acid, sucrose and urea, at varying concentrations, were tested as secondary plasticizers for the starch‐glycerol mixture. The ingredients were extruded at 110 and 120°C barrel temperatures to determine the effects of extrusion temperature, plasticizer type and their concentrations on the film‐forming characteristics of starch, as well as their effects on selected physical and functional properties of the films. The physical and mechanical properties of the films were studied by scanning electron microscopy (SEM) and tensile testing, while the glass transition and gelatinization properties were analyzed using differential scanning calorimetry (DSC). The interactions between the functional groups of starch and plasticizers were investigated using Fourier‐transform infrared (FTIR) spectroscopy. The water vapor permeability (WVP) properties of starch films were determined using ASTM standard E96‐95. Scanning electron micrographs exhibited the presence of native and partially melted starch granules in the extruded films. The tensile stress, strain at break and Young's modulus of starch films ranged from 0.9 to 3.2 MPa, 26.9 to 56.2% and 4.5 to 67.7 MPa, respectively. DSC scans displayed two glass transitions in the temperature ranges of 0.1 to 1°C and 9.6 to 12°C. Multiple melting endotherms, including that of amylose‐lipid complexes, were observed in the thermoplastic extrudates. The gelatinization enthalpies of the starch in the extruded films varied from 0 to 1.7 J/g, and were dependent largely on the extrusion temperature and plasticizer content. The shift in the FTIR spectral bands, as well as the appearance of double‐peaks, suggested strong hydrogen bonding interactions between the starch and plasticizers. The WVP of starch films ranged from 10.9 to 15.7 g mm h^‐1 m^‐2 kPa^‐1, depending on the extrusion temperature and the type of plasticizer used.     

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。     

Aging Effects on Sorbitol‐ and Non‐Crystallizing Sorbitol‐Plasticized Tapioca Starch Films

The effect of aging on the properties of tapioca starch films plasticized with either sorbitol (S) or non‐crystallizing sorbitol (NCS) was investigated in this study. Tapioca starch, plasticizer and deionized water were mixed, heated, cast on high‐density polyethylene plates and dried at ambient conditions. The results showed that S was more effective in plasticizing fresh starch film than NCS. However, sorbitol crystallization was observed in S‐plasticized starch film after one month of storage, while there was no crystallization observed in NCS‐plasticized starch film after two months of storage. Mechanical properties of both S‐ and NCS‐plasticized starch films changed significantly with time, but with less change in the NCS‐plasticized films. Tensile strength, elastic modulus and toughness increased over time; conversely, elongation decreased. Additionally, the water vapor transmission rate decreased as storage time increased. The fact that mechanical properties of both S‐ and NCS‐plasticized films changed is likely due to an increase in crystallinity of the starch in the films with time.     

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.