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.     

甘油与甲基纤维素对高直链玉米淀粉- 壳聚糖复合膜性能的影响

以高直链玉米淀粉(HACS)和壳聚糖(CS)为基本材料,甘油为增塑剂,甲基纤维素(MC)为增强剂制备可食性复合膜,研究高直链玉米淀粉与壳聚糖的质量比,甘油的添加量以及甲基纤维素的添加量对复合膜物理性能的影响,包括抗拉强度(TS)、断裂伸长率(E)、水蒸气透过系数(WVP)和色度。结果表明,壳聚糖添加量的增大与甘油添加量的增加都使高直链玉米淀粉- 壳聚糖复合膜的抗拉强度降低,断裂伸长率和WVP 显著增大,膜颜色变黄;甲基纤维素的添加改善了复合膜的机械性能和WVP,随着甲基纤维素添加量的增加,复合膜的抗拉强度和断裂伸长率都随之增大,WVP 逐渐降低,且对膜的颜色没有显著影响。     

Physical and Mechanical Properties of Durum Wheat (Triticum durum) Starch Films Prepared with A‐ and B‐type Granules

The use of starch for the production of biodegradable materials has been increasing. Wheat is an important source, however, durum wheat starch and its separated granular components had not been evaluated for this purpose. The aim of this study was to evaluate the physical and mechanical properties of durum wheat starch films when prepared with a distribution of different granular‐sized starches (A‐ and B‐type). Starch was isolated, and the A and B populations of granules were separated. Films were prepared by casting. Glycerol (G) was used as a plasticizer in concentrations of 25% and 40%, respectively. Starch films were evaluated using scanning electron microscopy (SEM), mechanical properties (tensile strength, TS, elongation at break, E, elastic modulus, EM), solubility, and X‐ray diffraction (XRD). Durum wheat starch films were transparent, flexible, and, according to SEM, highly homogeneous. Films prepared with 25% G showed brittle material behavior (TS = 42–50 MPa, E = 1.4–2.7%, and EM = 31–34 MPa), whereas those prepared with 40% G had ductile material characteristics (TS = 11–17 MPa, E = 4–41%, and EM = 4–11.3 MPa). These mechanical properties of the films were significantly affected by the glycerol concentration and the starch granule type used. The film solubility was low when compared to those reported in other studies. It increased with increasing plasticizer concentration. According to the XRD, the films showed a semi‐crystalline structure.     

Physical and Mechanical Properties of High-amylose Rice and Pea Starch Films as Affected by Relative Humidity and Plasticizer

ABSTRACT: The tensile properties, water vapor permeability, oxygen permeability at different relative humidities (RH), and water solubility of edible films made of high-amylose rice starch (RS) or pea starch (PS) were measured and compared with the most commonly used edible films. Photomicrography of starch films shows amylopectin-rich gels and amylose-rich granules. The addition of glycerol into starch films made amylose-rich granules swollen and continuously dispersed between amylopectin-rich gels. Tensile strength of RS and PS films decreased when RH increased from 51% to 90%, whereas elongation-at-break (E) of both films increased when RH increased. Water vapor permeabilities of both films were similar, resulting in 130 to 150 g mm/m²/d /kPa. Oxygen permeability of RS and PS were very low (< 0.5 cm³μm/m²/d/kPa) below 40% RH, and 1.2 to 1.4 at 45% RH. Water solubility of PS film was 32.0%, which is lower than that of RS film (44.4%). Overall high-amylose rice and pea starch films possess an excellent oxygen barrier property with extremely high stretchability.     

Permeability and Mechanical Properties of Cellulose-Based Edible Films

Factors affecting barrier properties [oxygen permeability (OP) and water vapor permeability (WVP)] and mechanical properties [tensile strength (TS) and elongation (E)] were investigated for methyl cellulose (MC) and hydroxypropyl cellulose (HPC) films. OP, WVP and TS of MC and HPC films increased as the molecular weight (MW) of the cellulose increased. E of MC films increased as MW increased, but E of HPC films was highest for the intermediate MW of 370,000. OP, WVP and TS of MC films were not a function of thickness, but E slowly increased as film thickness increased. OP and WVP of HPC films were not relatable to film thickness, but TS and E of HPC films slowly increased as film thickness increased. TS decreased and E increased for both film types as concentration of plasticizers was increased. Plasticizers enhanced or retarded OP and WVP of cellulose-based films, depending on their concentrations.     

Heat Curing of Soy Protein Films at Atmospheric and Sub-atmospheric Conditions

ABSTRACT: The effect of heat curing at atmospheric or subatmospheric conditions on selected properties (moisture content, water vapor permeability (WVP), color, tensile strength (TS), elongation (E), and total soluble matter (TSM) content) of cast soy protein isolate films was investigated. Films were heat cured at 85 °C for 6, 12, 18, or 24 h at absolute pressures of 101.3, 81.32, or 61.32 kPa. Heat-cured films had increased (P < 0.05) TS and decreased (P < 0.05) WVP and E compared to control, unheated films. Heat treatment under vacuum reduced the WVP of films faster than heat curing at atmospheric pressure. High TS values, low E values, and low TSM values were also reached within short heating time under vacuum. However, vacuum treatment increased the size and number of cavities in cured films as evidenced by scanning electron micrographs.     

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.     

Barrier properties of sodium caseinate films as affected by lipid composition and moisture content

This work analyses the effect of lipid addition (oleic acid, beeswax and oleic acid-beeswax mixtures) as well as the influence of the relative humidity (RH), or the equilibrium water content of the films, on the permeability of sodium caseinate based films to water vapor and gas (oxygen and carbon dioxide). The effect that lipid addition had on the gas and water vapor permeability was dependent both on the composition of oleic acid-beeswax mixtures and the film’s moisture content. The addition of lipid mixtures reduced water vapor transfer as compared to the control films (without lipid), whereas pure oleic acid or beeswax were less effective. Both control films and films prepared with pure beeswax showed the lowest O₂ and CO₂ permeability, whereas the incorporation of oleic acid exponentially increased these values. A linear increase in water vapor and gas permeability was observed when the water content of the film rose, due to its plasticizing effect, which led to an increase in the molecular mobility. Predictive equations for water vapor permeability (WVP) and gas permeability were established as a function of water content and lipid composition.     

Mechanical and water vapor barrier properties of tapioca starch/decolorized hsian-tsao leaf gum films in the presence of plasticizer

The objectives of this research were to examine the mechanical and water vapor barrier properties of the starch/decolorized hsian-tsao leaf gum (dHG) films as a function of dHG and glycerol concentration. Edible film-forming solutions were prepared by mixing tapioca starch with dHG at different starch/dHG ratios to make a total solid content of 2%. In total, 15–40% glycerol was then added based on the dry film matter. Starch/dHG films were obtained by casting. It was found that the puncture strength, tensile strength, and modulus as well as the inverse of relaxation coefficient of starch/dHG films pronouncedly increased with increasing dHG, accompanied with a decreasing tendency in puncture deformation and tensile strain at break. Such results implied that starch interacted with dHG synergistically, resulting in the formation of a new network to improve the mechanical properties of tapioca starch/dHG films. Mechanical strengths of starch/dHG films decreased and water vapor permeability (WVP) at 75% RH increased with increasing glycerol concentration. However, the plasticizing effect of glycerol became less significant at high dHG concentration, particularly for the puncture deformation and tensile strain at break of the films. Water sorption isotherm results indicated that significant water sorption would only occur at high water activity (about 0.75), and generally became more pronounced with increasing glycerol and dHG concentration, but to a lesser extent for the latter. Dynamic mechanical analysis revealed that the major glass transition of starch/dHG films occurred at about −50 °C.     

Development and characterization of cassava starch and soy protein concentrate based edible films

The sensory attributes, mechanical, water vapour permeability (WVP) and solubility properties of cassava starch and soy protein concentrate (SPC)‐based edible films of varying levels of glycerol were studied. Addition of SPC and glycerol up to 30% and 20%, respectively, reduced stickiness and improved colour and appearance of the films. Tensile strength (TS), elastic modulus (EM) and elongation at break (EAB) of films increased, while film solubility (FS) and WVP decreased with SPC and glycerol up to 50% and 20% level, respectively, ranging from 20.33 to 26.94 MPa (TS), 41.33 to 72.76 MPa (EM), 7.90 to 12.28 MPa (EAB), 15.07 to 31.90% (FS) and 2.62 to 4.13 g H₂O mm m^?2 day kPa (WVP). The TS, EAB and WVP were higher for the biofilms than for low‐density polyethylene and cellophane films.     

Effect of pH and addition of corn oil on the properties of whey protein isolate-based films using response surface methodology

Response surface methodology (RSM) was used to investigate pH and corn oil (CO) effects on the properties of films formed from whey protein isolate (WPI). Test films were evaluated for tensile strength (TS), puncture strength (PT), percentage elongation at break point (E), water vapour permeability (WVP) and oxygen permeability (OP). TS of WPI films increased with increasing pH, while addition of CO produced no trend. However, when WPI solution pH increased >10.0, film TS generally decreased with CO addition (>11%). E values increased dramatically with increasing levels of CO when pH for WPI solutions were >8.5. However, pH had no effect on E values. WPI solutions possessing high pH values (maximum pH value of 10.62) produced WPI films with the highest PT values. WVP had a quadratic relationship with pH and CO addition. OP had an inversely linear relationship with increasing pH (6.5–10.5) and a quadratic relationship with CO addition. Optimal pH (9.88) and CO level (2.93%), determined from physical test film data, were predicted by RSM.     

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.     

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 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.     

Whey protein-polysaccharide blended edible film formation and barrier, tensile, thermal and transparency properties

BACKGROUND: Films made from different protein (P) or polysaccharide (PS) materials have widely different properties. The objective of this study was to determine whether whey protein isolate (WPI)‐PS blended films possess a combination of properties intermediate and possibly superior to WPI or PS film alone. RESULTS: Oxygen permeability (OP) and tensile strength (TS) for PS‐WPI blended films were intermediate between the OP and TS properties of pure methycellulose (MC), hydroxypropylmethylcellulose (HPMC) or sodium alginate (SA) film and pure WPI film. Starch‐WPI blends gave the weakest films. Water vapor permeability values for all pure and blended films were similar. Blended films made of MC, HPMC or SA with WPI had lower transparency than pure MC, HPMC, SA or WPI films. Differential scanning calorimetry thermograms obtained from the blended films exhibited a single glass transition temperature (T_g) at an intermediate value between the T_g values of the pure films. CONCLUSIONS: Whether properties of PS‐WPI blended films are intermediate to properties of the pure PS and WPI film depends on the particular PS and specific property. In the case of MC or HPMC with WPI, the blended films reflect the higher TS of the PS and lower OP of the WPI. Copyright © 2011 Society of Chemical Industry     

Effect of plasticizer content on the functional properties of extruded gelatin-based composite films

Beef gelatin, in combination with varying levels of glycerol, was used to manufacture films by extrusion. A twin-screw co-rotating extruder was employed to produce the films and the mechanical and barrier properties of the films were investigated. Increasing the plasticizer content increased (P < 0.05) elongation at break (EAB) values but decreased (P < 0.05) tensile strength (TS) values. Oxygen permeability (OP) values for gelatin-based composite films increased (P < 0.05) as the concentration of glycerol increased. Additionally, the solubility of films in water and seal strength increased as glycerol content increased. FTIR results indicated that increasing glycerol concentration increased and displaced the peak situated around 1032 cm⁻¹, which corresponded to glycerol. Gelatin-based composite films with a concentration of 0.2% glycerol possessed the lowest water vapor permeability (WVP) and OP values. From the data generated in this study, it is clear that the use of a plasticizing agent in film formulations should be carefully considered because of the negative effects that the plasticizing agent could have on extruded film barrier properties.     

Starch–methylcellulose–whey protein film properties

Four % (wt/wt) aqueous solutions were prepared at corn starch:methylcellulose:whey protein isolate (CS:MC:WPI) ratios of 2:2:2, 1:2:3, 2:1:3, 2:2:0, 1:2:0 and 2:1:0. Glycerol (gly) was used as a plasticiser at CS–MC–WPI:gly ratios of 2:1, 2.5:1 and 3:1. CS–MC–WPI blend films were stronger than CS–WPI films and had lower oxygen permeability (OP) than MC–WPI films. The highest tensile strength (TS) of blend films was 8.01 ± 3.41 MPa, at CS:MC:WPI ratio of 2:2:0 and CS–MC–WPI:gly ratio of 3:1. Lowest OP value was 45.05 ± 7.24 cm³ μm m^?2 per day kPa^?1, at CS:MC:WPI ratio of 2:2:2 and CS–MC–WPI:gly ratio of 3:1. OP values were predictable based on relative amounts of components. However, TS and elastic modulus properties of the CS–MC–WPI blend films did not reflect the relative amounts of the components. All of CS–MC–WPI films were translucent indicating some degree of immiscibility among the CS, MC and WPI. These results indicate the influence of complex molecular interactions among the components.     

Effect of temperature and initial moisture content on sorption isotherms of banana dried by tunnel drier

Sorption isotherms of intermediate moisture content (IMC) products are essential to predict shelf-life of packaged moisture-sensitive product by modelling moisture uptake during storage and distribution. The effect of temperature and initial moisture content (MC) of IMC banana on the relationship between MC and water activity were investigated. Raw bananas were dried in a tunnel dryer at 2% relative humidity (RH), 70 °C, and a 3.2 ± 0.2 m s^–1 air velocity. Drying procedure was carried out a number of times until various IMC levels were obtained (5%, 14%, 22% and 33% db for banana). Sorption isotherms of bananas were determined at 10, 20, 30 and 40 °C. The initial MC of IMC banana had no significant effect on the relationship between MC and water activity according to statistical analysis. All the sorption curves were found to be Type II. BET, GAB, modified GAB, Oswin, Halsey and modified Freundlich models were fitted to the data and it was found that the best results were obtained with a modified Freundlich equation. A secondary modified Freundlich model was built accounting for the effect of a _w and temperature on the sample MC.     

Properties of Chitosan Films as a Function of pH and Solvent Type

ABSTRACT: Two different deacetylated chitosans were dissolved in formic, acetic, lactic, or propionic acid to prepare chitosan films. The pH values of the film-forming solutions were adjusted to 3, 4, and 5. Water vapor permeability (WVP), tensile strength (TS), elongation (E), and total soluble matter (TSM) were significantly ( P < 0.05) affected by acid type, pH, and degree of deacetylation (DA). Low DA (LDA) chitosan films had lower WVP and TSM, higher TS compared with high DA (HDA) chitosan films. The E values were not affected by DA. As pH increased, WVP and TSM of chitosan films tended to increase while TS decreased significantly ( P < 0.05). Chitosan films with acetic and propionic acid solvents had low WVP and TSM and high TS, while films with lactic acid solvent had high E and TSM and the lowest TS. Fourier-transform infrared showed peak shifting in the spectra with different solvents and at different pH values. Chitosan films with lactic acid solvent showed a peak shift to a lower frequency range. The NH₃⁺ band was absent in the pH 5.0 chitosan film spectra.     

Fatty Acid Concentration Effect on Tensile Strength, Elongation, and Water Vapor Permeability of Laminated Edible Films

Water vapor permeability (WVP), tensile strength (TS), and elongation (E) were investigated in laminated methyl cellulose/corn zein-fatty acid films. They were prepared by casting corn zein-fatty acid solutions onto methyl cellulose films. WVP decreased as chain length and concentration of fatty acids increased. The TS of laminated edible film containing palmitic acid decreased as palmitic acid increased. The TS of films containing stearic-palmitic acid blends showed similar trends but there were no significant differences among blends. The TS of the film containing lauric acid was maximum at 30% lauric acid concentration. The E values for films containing fatty acids varied inversely with TS.