Influence of hydrocolloid nature on the structure and functional properties of emulsified edible films

To investigate the influence of polymer behaviors on the structure and the functional properties of emulsified films, agar (AG) and cassava starch (CAS) were used as hydrocolloid continuous phases in which hydrogenated vegetable oil (VGB81) was dispersed. Different ratios of hydrophilic/hydrophobic materials (HB/HL) were also used in film formulations to study the evolution of film-emulsion structure. Microscopically observed, VGB–CAS emulsified films exhibit a similar bilayer structure. However, there was just a migration and an aggregation of lipid particles. There was no coalescence which could form a continuous “lipid layer” necessary for an effective barrier. Moreover, they could not be made with a HB/HL ratio greater than 0.7:1. Conversely, AG chains set into gel, which solidifies film-forming emulsion before drying, leading to a fixed macronetwork structure. Films made with a high HB/HL ratios lead to a film structure becoming like a multilayer system. The water vapor permeability of emulsified films is better found when HB/HL ≥ 1:1 when films are formed only with gelling polysaccharide (AG). In addition, there is no relationship between the moisture sorption and the moisture permeability of emulsified films. In contact with liquid water, brief sorption and swelling surface are observed for VGB–AG film surface and rapid absorption following a temporary hydrophobicity is found in the case of VGB–CAS films. While the mechanical properties of VGB–CAS films are strongly altered, those of VGB–AG films are considered to be sufficient for most of applications.     

Preparation and properties of rice starch–chitosan blend biodegradable film

Biodegradable blend films from rice starch–chitosan were developed by casting film-solution on leveled trays. The influence of the ratio of starch and chitosan (2:1, 1.5:1, 1:1, and 0.5:1) on the mechanical properties, water barrier properties, and miscibility of biodegradable blend films was investigated. The biodegradable blend film from rice starch–chitosan showed an increase in tensile strength (TS), water vapor permeability (WVP), lighter color and yellowness and a decreasing elongation at the break (E), and film solubility (FS) after incorporation of chitosan. The introduction of chitosan increased the crystalline peak structure of starch film; however, too high chitosan concentration yielded phase separation between starch and chitosan. The amino group band of the chitosan molecule in the FTIR spectrum shifted from 1541.15 cm⁻¹ in the chitosan film to 1621.96 cm⁻¹ in the biodegradable blend films. These results pointed out that there was a molecular miscibility between these two components. The properties of rice starch–chitosan biodegradable blend film and selected biopolymer and synthetic polymer films were compared; the results demonstrated that rice starch–chitosan biodegradable blend film had mechanical properties similar to the other chitosan films. However, the water vapor permeability of rice starch–chitosan biodegradable blend film was characterized by relatively lower water vapor permeability than chitosan films but higher than polyolefin.     

Physical‐Mechanical Properties of Agar/κ‐Carrageenan Blend Film and Derived Clay Nanocomposite Film

Abstract: Binary blend films with different mixing ratio of agar and κ‐carrageenan were prepared using a solution casting method with and without nanoclay and the effect of their composition on the mechanical, water vapor barrier, and water resistance properties was tested. The tensile strength (TS) of the κ‐carrageenan film was greater than that of agar film. The water vapor permeability (WVP) of the agar film was lower than that of κ‐carrageenan film, the swelling ratio (SR) and water solubility (WS) of κ‐carrageenan film were higher than those of agar film. Each property of the binary blend films varied proportionately depending on the mixing ratio of each component. The XRD result indicated that the nanocomposite with agar/κ‐carrageenan/clay (Cloisite^® Na⁺) was intercalated. Consequently, the mechanical strength, water vapor barrier properties, and water contact angle (CA) were significantly (P < 0.05) improved through nanocomposite formation.     

Tuning the Functional Properties of Polysaccharide–Protein Bio‐Based Edible Films by Chemical,Enzymatic, and Physical Cross‐Linking

Among natural biopolymers, polysaccharides and proteins are very promising for biodegradable and edible wraps with different characteristics, so that their formulations can be tailor‐made to suit the needs of a specific commodity. Films prepared from polysaccharides have good gas barrier properties but exhibit lower resistance to moisture compared to protein films (edible) or polylactide films (biodegradable). Protein‐based films show better mechanical and oxygen barrier properties compared to polysaccharide films. For that reason, film performances may be enhanced by producing blend systems, where hydrocolloids (mixtures of proteins and/or polysaccharides) form a continuous and more cohesive network. However, the lower water barrier properties of hydrocolloid films and their lower mechanical strength in comparison with synthetic polymers limit their applications in food packaging. Therefore, the enhancement of biopolymer film properties has been studied to attain appropriate applications. This review provides an extensive synthesis of the improvement of the properties of edible polysaccharide–protein films by way of various chemical, enzymatic, and physical methods. These methods primarily aim at improving the mechanical resistance. They also permit to ameliorate the water and gas barrier properties and related functional properties.     

Composite and bi-layer films based on gelatin and chitosan

The aims of this work were: to develop composite, bi-layer and laminated biodegradable films based on gelatin and chitosan, to determine film barrier and mechanical properties and to characterize their microstructure.Gelatin and chitosan concentrations used were 7.5% and 1% (w/w), respectively. Glycerol (0.75%) was added as plasticizer.Physicochemical properties such as moisture content, transparency and color were analyzed. Composite and bi-layer systems showed a compact structure indicating a good compatibility between components.Water vapor permeability (WVP) was independent of film thickness up to 120 μm for gelatin films and 60 μm for chitosan ones. Both, bi-layer and laminated systems resulted effective alternatives to reduce WVP of composite films (at least 42.5%). Bi-layer systems showed better mechanical properties than laminated ones. The resistance at break increased from 54.3 for composite to 77.2 MPa for bi-layer films, whereas elongation at break values of both composite and bi-layer films were similar (2.2–5.7%).     

大豆蛋白和羧甲基葡甘聚糖共混膜的制备和性能

为了提高大豆蛋白膜的机械和阻湿性能,制备了大豆分离蛋白/羧甲基葡甘聚糖共混膜。用红外光谱、透光率测试、扫描电镜测定表征了其结构,测试了共混膜的力学、抗潮、阻气等性能。结果表明,大豆分离蛋白与羧甲基葡甘聚糖有良好的相互作用,共混膜的力学性能、抗潮性能及阻气性能均有明显提高,其中拉伸强度较羧甲基葡甘聚糖提高了117.6%,吸湿增重较羧甲基葡甘聚糖下降了19.02%,透湿系数下降了40.97%。     

Water vapour barrier and tensile properties of composite caseinate-pullulan films: Biopolymer composition effects and impact of beeswax lamination

The water sorption, water barrier properties and mechanical behaviour of pullulan (P) and sodium caseinate (SC), as well as their blend and bilayer films plasticized with sorbitol (25% dry basis), were investigated as a function of weight polymer ratio, water content and beeswax lamination. Very similar moisture sorption isotherms were obtained for blend and bilayer films with P/SC weight ratio of 1/3 and 3/1. Neither the type of film (blend or bilayer) nor the different P/SC ratio affected significantly (P > 0.05) the water vapour permeability (WVP) of the films. A mixture-process variable experimental design was applied to evaluate the effect of the proportion of the two polymers in relation with the relative humidity (RH, 53% and 75%) on the mechanical properties of the films. Increasing the P/SC ratio decreased the Young’s modulus (E), the tensile strength (σ_max) and increased the % elongation at break (% EB), suggesting that P imparts flexibility and SC stiffness to the composite films. With moisture content increase from 5% to 8% most of the films exhibited an increase in E and σ_max, whereas a sharp decline in both parameters and an increase in % EB were observed above this moisture level. The brittle to ductile transition of P coincided with its glass to rubber transition, whereas SC exhibited a ductile behaviour within the glassy state. The tensile characteristics of bilayer films at moisture content greater than 8% were dominated by the component present in higher proportion, while films made with the biopolymer blends showed mechanical behaviour closer to that of plain P films. Beeswax lamination of plain, bilayer and blend films resulted in a drastic decrease in water vapour permeance, whereas its effect on E and σ_max and in % EB was related to the mechanical properties of the hydrocolloid layers used and varied according to the moisture content of the films.     

Microstructure and mechanical properties of soy protein/agar blend films: Effect of composition and processing methods

The present work prepared a series of soy protein isolate/agar blend films containing 33% glycerol as plasticizer by solution casting and thermo-molding methods. The microstructure and mechanical properties of the blend films were evaluated in relation to the agar/protein ratio as well as the processing methods. Experimental results revealed that hydrogen bonding interactions existed between soy protein and agar. The casting films possessed more homogeneous interfaces compared with the molding films, leading to the superior mechanical properties than those molding films. Owing to the rigid three-dimensional network formed by the agar, the tensile strength of casting blend films was enhanced. With the increase of agar in the casting blend films, the crosslinking density increased and was responsible for the variations in tensile strength.     

Characterization of quinoa protein–chitosan blend edible films

Quinoa protein/chitosan films were obtained by solution casting of blends of quinoa protein extract (PE) and chitosan (CH). Films from a PE/CH blend were characterized by FTIR, X-ray diffraction, thermal analysis, and SEM. The tensile mechanical, barrier, and sorption properties of the films were also evaluated. The blend of PE with CH yielded mechanically resistant films without the use of a plasticizer. The film had large elongation at break, and its water barrier properties showed that they were more hydrophilic than CH film. The thickness and water-vapor permeability of PE/CH (v/v) 1/1 blend film increased significantly compared to pure CH films. CH films are translucent in appearance and yellowish in blend with PE. By blending anionic PE with cationic CH an interaction between biopolymers was established with different physicochemical properties from those of pure CH. Drying and sorption properties show significant differences between PE/CH blend film and CH film. The structural properties determined by XRD, FTIR and TGA showed a clear interaction between quinoa proteins and CH, forming a new material with enhanced mechanical properties.     

纳米粒子对多糖基复合膜微观结构的影响研究进展

多糖基复合膜具有均匀、透明和可降解等特点,成为生物可降解膜领域的热点研究内容。研究发现,纳米粒子与多糖溶液共混能形成复杂的成膜液,干燥成膜后,膜的原生微观结构改变,进而改善复合膜的力学、阻隔等性能。本文简述了淀粉膜、壳聚糖膜和魔芋葡甘聚糖膜三种多糖膜的微观结构及组分分子间的相互作用,并对纳米粒子与多糖共混成膜后,复合膜微观结构和理化性能的变化进行了重点阐述,以为多糖基复合膜微观结构设计与膜性能调控研究等提供参考。     

Physicochemical,Water Vapor Barrier and Mechanical Properties of Corn Starch and Chitosan Composite Films

Biodegradable flexible films were developed from corn starch (CS) and chitosan (CH); their microstructure, mechanical and barrier properties were evaluated. Chitosan and starch blend filmogenic suspensions showed a pseudoplastic behavior, similar to that of chitosan solutions. Smooth surfaces, homogeneous and compact film structures were observed from microstructure studies using scanning electron microscopy (SEM). The addition of glycerol reduced film opacity and increased film solubility of both CS and composite CS‐CH films. Water vapor permeability values of composite CS‐CH films plasticized with glycerol ranged between 3.76 and 4.54× 10⁻¹¹ g s⁻¹ m⁻¹ Pa⁻¹, lower than those of the single component films. CS‐CH films were resistant and their flexibility increased with glycerol addition. Tensile strength values of CS‐CH films were comparable to those of low‐density and high‐density polyethylenes but lower than that obtained for cellophane, however, composite biodegradable films showed lower elongation at break values than the synthetic commercial ones. In conclusion, CS‐CH films can be described as biofilms with a homogeneous matrix, stable structure and interesting water barrier and mechanical properties, with great possibilities of utilization, and with the advantage of biodegradability.     

Rheological,mechanical and moisture sorption characteristics of cassava starch‐konjac glucomannan blend films

Cassava starch (ST)‐konjac glucomannan (KGM) blend films were prepared and their thermal, rheological, mechanical, moisture sorption properties and water vapour transmission rate were determined. Response surface methodology was employed for the preparation of films using different levels of ST, KGM and glycerol. All the filmogenic solutions exhibited shear thinning behaviour. Apparent viscosity and the dynamic rheological properties of filmogenic solutions varied considerably with KGM content. Rheological analysis revealed that the blend films are more appropriate than neat ST film for controlled drug release studies and for food coating. The melting temperature and enthalpy of fusion of the blend films were lower than that of neat ST film. When compared to neat starch film, the blend films showed broader peaks in DSC patterns, which suggests that incorporation of KGM decreased the crystallinity of ST. Mechanical properties, elongation at break and tensile strength of blend films were significantly higher (112.8% and 22.5 MPa, respectively) than those of neat ST film. Due to the more hydrophilic nature of KGM when compared to ST, the WVTR and moisture absorption of blend films were greater than that of neat ST film. Though KGM is more hydrophillic in nature, blend films with higher amount of KGM (0.643g) showed comparably lower values for both WVTR and moisture absorption than other blends. The solubility of the blend films was lower than that of neat starch film which also confirmed the strong intramolecular attraction between ST and KGM.     

Sorption Characteristics of Soy Protein Films and their Relation to Mechanical Properties

Effects of plasticizers (glycerol, sorbitol, and 1:1 mixture of glycerol and sorbitol) on moisture sorption characteristics of hydrophilic soy protein isolate (SPI) films were investigated at three levels of plasticizer concentration (0.3, 0.5, and 0.7 g plasticizer/g SPI). The combined effects of relative humidity and plasticizer on mechanical properties of soy protein films were also examined. Moisture affinities of soy protein films were affected by hydrophilicity of plasticizer and its concentration. Under given RH conditions, films with higher glycerol ratio absorbed more moisture with higher initial adsorption rate, and films with higher plasticizer contents exhibited higher equilibrium moisture contents. Monolayer moisture contents of SPI films increased as glycerol ratio in a plasticizer mixture and plasticizer concentration increased. Plasticizer and absorbed water loosened the film synergistically, resulting in higher elongation but lower tensile strength. RH effects on mechanical properties of SPI films were varied with plasticizers and their concentration. Films of lower glycerol contents were more sensitive to RH variation as compared to the higher glycerol samples, whereas sorbitol concentration affected the RH region where a sharp decrease in TS value occurred.     

Physical properties of edible modified starch/carboxymethyl cellulose films

Novel modified starch/carboxy methyl cellulose (CMC) composite films were prepared by a casting method. The effects of CMC addition on the some physical properties of the resulted blend films were investigated. The blend film composed of 15% W/W CMC /starch, showed the lowest water vapor permeability (WVP) value (2.34 × 10⁻⁷ g/m^.h^.Pa).The moisture absorption and solubility in water properties of the blend films exhibited similar trends. The addition of CMC at the level of 20% W/W starch caused an increase in the ultimate tensile strength (UTS) by more than 59% in comparison to the pure starch film without any significant decrease in the strain to break (SB). The measurement of color values showed that by the increasing of the CMC content in polymer matrix, the b values (yellowness), YI and ∆E of the blend films decreased and the L values (Lightness) and WI index increased.

Industrial relevance

Ecological concerns have resulted in a renewed interest in natural and compostable materials, and therefore issues such as biodegradability and environmental safety are becoming important. Tailoring new products within a perspective of sustainable development or eco-design, is a philosophy that is applied to more and more materials. It is the reason why material components such as natural fibres, biodegradable polymers can be considered as interesting – environmentally safe – alternatives for the development of new biodegradable composites.Development of biodegradable materials based on starch has become a very attractive option and production of starch based plastic are gradually obtained considerable concern in the world.In this research, improvement of starch film properties is investigated.     

Effect of calcium and sodium caseinates on physical characteristics of soy protein isolate–lipid films

The effect of addition of caseinates to soy protein isolated (SPI) based films containing lipids (33% of oleic acid or 85:15 oleic acid (OA)–beeswax blend (BW)) on water vapour permeability (WVP), mechanical and optical properties was evaluated. SPI–lipids was combined with caseinates (sodium or calcium) in different SPI:caseinate ratios with the aim of improving water vapour barrier, mechanical and optical properties of SPI films containing lipids. Caseinate incorporation to SPI based films provoked an increase of elastic modulus and tensile strength at break, mainly for calcium caseinate. Both caseinates contributed to increase the water vapour barrier properties of soy protein-based films. Caseinates also provoked an increase of transparency of SPI based films and colour softening. The most effective combination was 1:1 sodium caseinate:SPI ratio, when film contains 85:15 oleic acid:beeswax ratio.     

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.     

Properties and release kinetics of pine bark incorporated agar and carrageenan film

Effects of plasticisers (glycerol, sorbitol and polypropylene glycol) and blend ratios on release behaviour, molecular vibration, mechanical and water barrier properties in agar and carrageenan films incorporating pine bark extract were investigated. Infrared spectra indicated hydrogen bonding of sorbitol and polypropylene glycol with film polymers which improved water diffusion and agar solubility but showed no effect in carrageenan films due to high water affinity. Hydrophilicity of the plasticisers modified dissolution of films and strongly affected the release behaviours of polyphenols and antioxidant capacity (DPPH• and FRAP). Film solubility showed high correlation to release behaviours. Fick’s diffusion kinetics fitted well to release behaviour of pine bark to aqueous media (water, 3% acetic acid and 10% ethanol). Agar gave a higher diffusion coefficient that was improved by the addition of sorbitol and polypropylene glycol. Increased diffusion coefficients enhanced degree of release, with some diversions suggesting that solvent modified matrices and, hence, release properties.     

Preparation and properties of pullulan–alginate–carboxymethylcellulose blend films

Pullulan, alginate, and carboxymethylcellulose (CMC) films were solvent cast from aqueous polymer solution. At 55% RH and 20 °C, their tensile strength and elongation at break were 67 MPa and 11%, 49 MPa and 5.2%, and 45 MPa and 5.8%, respectively. Pullulan films had lower water vapor permeability than alginate and CMC films (4.4 × 10⁻⁷, 9.7 × 10⁻⁷, and 1.3 × 10⁻⁶ g m/Pa h m², respectively), but dissolved in water quicker than alginate and CMC films. By incorporating alginate and CMC into pullulan, water barrier and mechanical properties were weakened significantly. Blending pullulan with alginate or CMC up to about 17–33% (w/w total polymer) reduced film solubilization time in water. The addition of glycerol further reduced tensile strength, increased elongation at break, weakened water barrier properties, but enhanced solubilization in water. FTIR results indicated that blending pullulan with alginate and CMC resulted in weaker hydrogen bonds acting on –OH groups compared to the pure pullulan.     

Potato starch edible films to control oxidative rancidity of polyunsaturated lipids: effects of film composition, thickness and water activity

The objective of this work was to study the effect of potato starch-based films acting as oxygen barrier on the oxidative rancidity of vegetable oil, as an example of a food rich in polyunsaturated fatty acids. The effect of glycerol (Gly) content (0%, 10%, 20%, 30%), film thickness (30, 60, 100 μm) as well as environmental relative humidity (RH) (50% or 75%) were analysed. Results obtained confirmed that potato starch films delayed the rancidity in vegetable oil. Films without Gly provided the same protection as films with 10% Gly. Films with higher Gly content were not as effective oxygen barrier. It is likely that the fact that film protective capability diminished with increased RH or Gly content was due to the increasing moisture content of the films. Despite that fact, potato starch films can be considered a very efficient oxygen barrier even at RH as high as 75%.     

Barrier and Tensile Properties of Transglutaminase Cross-linked Gelatin Films as Affected by Relative Humidity, Temperature, and Glycerol Content

Gelatin films were prepared by enzymatic cross-linking with transglutaminase, and their mechanical and barrier properties were evaluated as functions of relative humidity (RH, 30 to 75%), temperature (15 to 35°C) and glycerol content (15 to 31%). Water and glycerol plasticized the films synergistically, resulting in greater elongation but lower tensile strength values. Films with higher glycerol contents exhibited higher moisture contents, indicating higher hydrophilicity of the films. Permeabilities of oxygen and allyl isothiocyanate (an antimicrobial vapor from Cruciferae plants) were low when the films were dry, but increased considerably when RH>50%. Therefore, RH conditions during end-use applications must be considered to optimize the performance of these films.