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.     

Mechanical, water vapor barrier and thermal properties of gelatin based edible films

Edible films are thin materials based on a biopolymer. The objectives of this work were to determine the water vapor permeability and the mechanical and thermal properties of edible films based on bovine hide and pigskin gelatins. These films were prepared with 1 g of gelatin/100 ml of water; 15–65 g sorbitol/100 g gelatin; and at natural pH. The samples were conditioned at 58% relative humidity and 22°C for 4 days before testing. The mechanical properties were determined by the puncture test and the water vapor permeability by gravimetric method at 22°C. For DSC analysis, samples were conditioned over silica gel for 3 weeks. Samples (10 mg) were heated at 5°C/min, between −150 and 150°C in a DSC TA 2010. A second scan was run after cell cooling with liquid nitrogen. As expected, the puncture force decreased and the puncture deformation and water vapor permeability increased with the sorbitol content. The origin of gelatin was important only above 25 g sorbitol/100 g gelatin. The DSC traces obtained in the first scan of samples with 15–35 g sorbitol/100 g gelatin, showed a well visible glass transition followed by a sol–gel transition. However, with the increase of sorbitol concentration, the glass transition became broader, typical of the system presenting a phase separation. The model of Couchman and Karazs for ternary system, was used to predict the Tg values as a function of sorbitol concentration.     

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.     

Effects of partial hydrolysis and plasticizer content on the properties of film from cuttlefish (Sepia pharaonis) skin gelatin

Properties of film from cuttlefish (Sepia pharaonis) ventral skin gelatin with different degree of hydrolysis (DH: 0.40, 0.80 and 1.20%) added with glycerol as plasticizer at various levels (10, 15 and 20%, based on protein) were investigated. Films prepared from gelatin with all DH had the lower tensile strength (TS) and elongation at break (EAB) but higher water vapor permeability (WVP), compared with the control film (without hydrolysis) (p < 0.05). At the same glycerol content, both TS and EAB decreased, while WVP increased (p < 0.05) with increasing %DH. At the same DH, TS generally decreased as glycerol content increased (p < 0.05), however glycerol content had no effect on EAB when gelatins with 0.80 and 1.20% DH were used (p > 0.05). DH and glycerol content had no marked impact on color and the difference in color (ΔE^∗) of resulting films. Electrophoretic study revealed that degradation of gelatin and their corresponding films was more pronounced with increased %DH, resulting in the lower mechanical properties of films. Based on FTIR spectra, with the increasing %DH as well as glycerol content, higher amplitudes for amide-A and amide-B peaks were observed, compared with film from gelatin without hydrolysis (control film) due to the increased –NH₂ group caused by hydrolysis and the lower interaction of –NH₂ group in the presence of higher glycerol. Thermo-gravimetric analysis indicated that film prepared from gelatin with 1.20% DH exhibited the higher heat susceptibility and weight loss in the temperature range of 50–600 °C, compared with control film. Thus, both chain length of gelatin and glycerol content directly affected the properties of cuttlefish skin gelatin films.     

Preparation and properties of dialdehyde carboxymethyl cellulose crosslinked gelatin edible films

Glycerol-plasticized gelatin edible films with a new kind of dialdehyde polysaccharide, dialdehyde carboxymethyl cellulose (DCMC) as crosslinking agent are successful prepared using casting techniques. The mechanical properties, thermal stability, light barrier properties, swelling behavior as well as water vapor permeability (WVP) of the gelatin-DCMC films are investigated. The results indicate that the addition of DCMC causes tensile strength (TS) and thermal stability to increase and elongation at break (EB) to decrease, suggesting the occurrence of crosslinking between gelatin and DCMC. The light barrier measurements present high values of transparency at 280 nm and low values of transparency at 600 nm of the gelatin-DCMC films, indicating that gelatin-DCMC films are very transparent (lower in transparency value) while they have excellent barrier properties against UV light. Moreover, the values of transparency at 280 nm increase with the increased DCMC and glycerol content, suggesting the potential preventive effect of gelatin-DCMC films on the retardation of product oxidation induced by UV light. Furthermore, the addition of DCMC can greatly decrease the water vapor permeability (WVP) and equilibrium swelling ratio (ESR) down to values about 1.5 × 10⁻¹⁰ g m/m² s Pa and 150%, revealing the potential of DCMC in reducing the water sensitivity of gelatin-based films. In common for hygroscopic plasticizer in edible films, the addition of glycerol gives increase of EB and WVP and decrease of thermal stabilities and ESR of the gelatin-DCMC films.     

Stability enhancement of shellac by formation of composite film: Effect of gelatin and plasticizers

The objective of the present study was to reduce the polymerization of shellac by the formation of composite films with gelatin. The 6% w/w of composite film based on shellac and gelatin was prepared by the incorporation of different concentrations of gelatin and was prepared by film casting method. The stability of the composite films was then studied at 40 °C, 75% RH for 180 days in a stability chamber and the physicochemical properties were investigated. The results demonstrated that the higher concentrations of gelatin (30%, 40% and 50%) contributed to slight change in the acid value and the percentage of insoluble solids upon 180 days of storage. These results were due to the protection at the active sites of the shellac, carboxyl and hydroxyl groups, by the electrostatic interaction between the negative charge of shellac and the positive charge of gelatin, resulting in the stabilized shellac. However, the mechanical properties could not withstand the storage time; further investigation was required to improve the stability in terms of mechanical properties of the composite film by the addition of a plasticizer. Two types of plasticizers were used: polyethylene glycol (PEG) and diethyl phthalate (DEP) represented hydrophilic and hydrophobic plasticizers at the concentrations of 5% and 10%, respectively. The addition of both types and concentrations of plasticizers could improve the poor mechanical properties and brittleness of the composite film for a longer storage time. However, only PEG 400 at 5% and 10% w/w acted as a good plasticizer capable of improving the stability of the composite film under the longer periods of storage. Therefore, the attempt to improve the stability in terms of polymerization and mechanical properties of shellac by the formation of the composite film and the addition of the plasticizer could be achieved. The result could be used to develop a new material for the various applications of edible films for coating in food and pharmaceutical industries.     

An approach for the enhancement of the mechanical properties and film coating efficiency of shellac by the formation of composite films based on shellac and gelatin

The purpose of this study was to enhance the mechanical properties and film coating efficiency of shellac by the formation of composite films with different concentrations of gelatin. The composite films were prepared by the casting method and their mechanical and physicochemical properties were investigated. The results demonstrated that the puncture strength and percentage elongation of the composite film increased from 3.61 to 15.58 MPa and from 3.80% to 32.47% as the gelatin concentration increased to 50% w/w, respectively, indicating the enhancement of the strength and flexibility of the shellac film. The efficiency of the composite film over two model substrates, i.e., hydrophilic and hydrophobic substrates, respectively, was also studied. The work of adhesion and spreading coefficient of the composite film increased from 66.42 to 83.53 mN/m and from −8.14 to −3.07 mN/m for the hydrophilic substrate, indicating the improvement of the coating efficiency whereas the hydrophobic substrate showed the opposite trend with the increase in gelatin concentration. Therefore, the formation of the composite film not only improved the mechanical properties of shellac but also enhanced the efficiency of film coating by the modification of different concentrations of hydrocolloid polymer to suit with the type of coating substrate. Hence the knowledge of composite film could make beneficial contributions to the various applications in film coating for the food and pharmaceutical industries.     

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.     

Physical, mechanical, and barrier properties of carp and mammalian skin gelatin films

Films of 0.11 to 0.13 mm thickness were prepared using gelatins from the skins of cultured freshwater carp species and mammalian gelatins viz., porcine and bovine skin gelatin. A comparative study was made on the physical, mechanical, and barrier properties of these films. The amino acid composition, gel strength, clarity, and gel setting point of the gelatins were also determined. Carp skin gelatins had a lower imino acid content (19.16% to 20.86%) than mammalian skin gelatins (22.91% to 23.7%). Grass carp gelatin had gel strength of 230.2 B that is comparable to the reported value for bovine skin gelatin (227.2 B). The bloom values of rohu and common carp skin gelatins were 188.6 B and 181.3 B, respectively, which were significantly lower than mammalian gelatins. Mammalian gels have significantly higher (P < 0.05) setting temperatures (23.7 to 24.2 °C) than carp skin gelatins. Tensile strength (TS) was lowest for films from common carp and rohu skin gelatin (490 and 497 kg/cm(2), respectively) and highest for porcine skin gelatin film. The degree of transparency (L*) was significantly higher for films from grass carp, bovine hide, and pork skin gelatin films. Carp skin gelatin films had significantly lower water vapor permeability (WVP) and oxygen permeability (OP) than mammalian skin gelatin films, which indicated that carp skin gelatin based films have superior barrier properties than mammalian skin gelatin films.     

Effects of plasticizers on thermal properties and heat sealability of sago starch films

Sago starch films were plasticized with sorbitol, glycerol, or a combination of sorbitol/glycerol (1:1, 1:3, and 3:1 ratios) and the effects on the thermal properties and heat sealability of the films were investigated. Films were sealed with an impulse heat sealer at a dwell time of 1 s and temperature of 110 ± 10 °C. Thermal properties of the films (determined using a differential scanning calorimeter) showed that onset temperatures (T_o) of sorbitol-plasticized films were significantly lower than those of glycerol-plasticized films. All films were heat sealable, but sorbitol-plasticized films exhibited better heat sealability than did the glycerol type. The highest seal strength was obtained with a 3:1 combination of sorbitol/glycerol. In summary, the type of plasticizer governed the heat sealability as well as the seal strength of starch films.     

Effect of cellulose fibers addition on the mechanical properties and water vapor barrier of starch-based films

Starch-based films have promising application on food packaging, because of their environmental appeal, low cost, flexibility and transparency. Nevertheless, their mechanical and moisture barrier properties should be improved. The aim of this work was to enhance these properties by reinforcing the films with cellulose fibers. Besides, the influences of both the solubility coefficient of water in the films (β) and the diffusion coefficient of water vapor through the films (D^w) on the films' water vapor permeability (K^w) were investigated. Films were prepared by the so-called casting technique, from film-forming suspensions of cassava starch, cellulose fibers (1.2 mm long and 0.1 mm of diameter), glycerol and water. The influence of fibers addition on K^w was determined at three relative humidity gradient ranges, ΔRH (2–33%, 33–64% and 64–90%). Films reinforced with cellulose fibers showed higher tensile strength and lower deformation capacity, and presented lower K^w than films without fibers. K^w showed strong dependency of β and D^w, presenting values up to 2–3 times greater at ΔRH = 64–90% than at ΔRH = 33–64%, depending on the film formulation. Therefore, adding cellulose fibers to starch-based films is a viable alternative to improve their mechanical and water barrier properties. Besides, this work showed the importance of determining film's water vapor permeability simulating the real environmental conditions the film will be used.     

Stability of the mechanical properties of edible films based on whey protein isolate during storage at different relative humidity

Formulations for whey protein isolate (WPI)-based films include low molecular weight plasticizers, which implies certain degree of instability of films properties due to plasticizer migration. The aim of this work was to study the effect of storage time on the mechanical properties of WPI films plasticized with two low molecular weight polyols: glycerol (Gly) and sorbitol (Sor). Films were stored inside cabins at 50% or 75% relative humidity (RH) and at room temperature. Mechanical properties and moisture content were measured at regular intervals for 30 weeks. The effect of plasticizer type and content and RH on mechanical properties right after equilibrium (1 week) was also included in this study.     

Functional properties of films based on soy protein isolate and gelatin processed by compression molding

Soy protein isolate (SPI) based films, blended with gelatin and plasticized with glycerol at pH 10, were prepared by compression molding with the aim to obtain environmentally friendly materials for packaging applications. Different contents and types of gelatin were incorporated into SPI-based mixtures to improve mechanical properties. All films obtained were flexible and transparent. Films with 15% of bovine gelatin showed higher tensile strength and similar elongation at break compared with the ones without gelatin. Moreover, contact angle measurements showed that the addition of gelatin decreased the hidrophilicity of the films, while UV barrier properties were maintained. The effect of gelatin addition has been explained using Fourier transform infrared (FTIR) and the changes observed in the intensity of the bands corresponding to the amide group showed that gelatin interacts with SPI, which was confirmed by the decrease of total soluble matter.     

Use of beef,pork and fish gelatin sources in the manufacture of films and assessment of their composition and mechanical properties

This study investigated the properties of different types of gelatin films from solutions of varying gelatin concentrations (4–8 wt %). Gelatin derived from beef, pork and fish skin sources was used to manufacture films using a casting approach. Mechanical properties of gelatin films, water vapour permeability (WVP), oxygen permeability, oil permeability and aqueous solubility of films were evaluated. FTIR spectroscopy was utilized to assess the composition of various gelatin sources so as to determine differences in composition of these sources and ultimately, in overall functionality. High concentration gelatin films had good mechanical properties with tensile and puncture strengths being particularly improved. Gelatin films manufactured from fish skin had the lowest WVP values for each concentration used. All gelatin films possessed excellent barriers to oxygen and oil. Films derived from pork gelatin exhibited lowest water solubility compared to those formed using beef and fish gelatin sources, regardless of the concentrations used. FTIR spectra showed that plasticizer and gelatin were well mixed and interacted well together. The use of higher concentrations of gelatin had the effect of increasing the wavenumber of amide-A in films due to greater interaction occurring between gelatin functional groups.     

Tensile and water barrier properties of cassava starch composite films reinforced by synthetic zeolite and beidellite

Composites films were prepared by the casting method using native cassava starch plasticized with glycerol and 3D or 2D synthetic fillers i.e. Beta zeolite and Na-beidellite type 2:1 phyllosilicate. Special attention was paid to the effect of the filler contents and type on the mechanical and barrier properties. It was shown that films reinforced with lyophilized Beta zeolite presented both high water solubility (WS) and water vapor permeability (WVP) values than the pristine starch whereas an improvement on the WVP was found for composites prepared from Na-beidellite or from non lyophilized Beta zeolite. For the two types of fillers, a drastic increase of the mechanical properties (especially in the Young’s modulus) was observed.     

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.     

Starch-gelatin edible films: Water vapor permeability and mechanical properties as affected by plasticizers

Physical and mechanical properties of edible films based on blends of sago starch and fish gelatin plasticized with glycerol or sorbitol (25%, w/w) were investigated. Film forming solutions of different ratios of sago starch to fish gelatin (1:0, 2:1, 3:1, 4:1, and 5:1) were used and cast at room temperature. Amylose content of sago starch was between 32 and 34% and the protein content of the fish gelatin was found to be 81.3%. The findings of this study showed that the addition of fish gelatin in starch solutions has a significant effect (p < 0.05), resulting in films with lower tensile strength (TS) and higher water vapor permeability (WVP). On the other hand, increasing protein content (from 10.9% to 21.6%) in film samples plasticized with sorbitol showed significantly lower (p < 0.05) TS but no trend was observed in % elongation-at-break (EAB) and no differences in WVP. However, TS decreased with higher protein content in the samples when either plasticizers were used in general, but no significance differences was observed among the samples (p < 0.05) with glycerol with exception to film with high protein content (21.6%) only and no trend was observed in % EAB among samples as well. Significant difference (p < 0.05) was observed in TS and viscosity between different formulations with sorbitol. The morphology study of the sago starch/fish gelatin films showed smoother surfaces with decreasing protein in the samples with either plasticizer. DSC scans showed that plasticizers and protein content incorporated with sago starch films reduced the glass transition temperature (T_g) and melting temperature (T_m) and the melting enthalpy (ΔH_m). In this study, observation of a single T_g is an indication of the compatibility of the sago starch and fish gelatin polymers to form films at the concentration levels used.     

Effects of essential oil on the water binding capacity,physico-mechanical properties,antioxidant and antibacterial activity of gelatin films

Gelatin films were prepared from gelatin solutions (10% w/v) containing Zataria multiflora essential oil (ZMO, 2, 4, 6 and 8% w/w of gelatin). Scanning electron microscopy observations indicate that ZMO droplets were well dispersed in the film matrix. Water solubility, water swelling, water uptake, water vapor permeability, tensile strength, elongation at break and Young's modulus for gelatin films were 27 ± 0.8%, 391 ± 11%, 135 ± 5%, 0.22 ± 0.014 g mm/m² kPa h, 4.4 ± 0.4 MPa, 125 ± 7% and 8.8 ± 0.4 MPa, respectively. Incorporation of ZMO into gelatin films caused a significant decrease in swelling and water uptake and increase in solubility and water vapor permeability, a significant decrease in tensile strength, increase in elongation at break, decrease in Young's modulus of the films, dose-dependently. Gelatin/ZMO showed UV–visible light absorbance/transmission ranging from 280 to 480 nm with maximum absorbance at 420 nm. Gelatin films exhibited very low antioxidant activity while, gelatin/ZMO films exhibited excellent antioxidant properties. The gelatin/ZMO films also exhibited excellent antibacterial properties against both Gram-positive and Gram-negative bacteria. Our results suggested that the gelatin/ZMO films could be used as an active film due to its excellent antioxidant and antimicrobial properties for food packaging applications.     

Naturally crosslinked gelatin gels with modified material properties

Natural crosslinking of gelatin using a simple plant-derived phenolic compound, caffeic acid has been studied. For the first time, we are reporting a thermo-irreversible gelatin gel formation at 60 °C. Controlling the crosslinking reaction has resulted in obtaining gelatin with modified material properties. Reaction parameters such as reaction pH, reaction time and concentration of caffeic acid have been optimised to obtain different degrees of crosslinking. The modified material properties were studied using small and large deformation rheology. Gelatin crosslinked at 60 °C and pH 9 for 20 min using 1.5% concentration of caffeic acid showed higher melting and setting temperatures. The storage modulus and gel strength were also found to be higher for crosslinked gelatin at higher temperatures.     

Evaluation of mechanical and water barrier properties of transglutaminase cross‐linked zein films incorporated with oleic acid

In this study, four concentrations of transglutaminase were used in zein films incorporated with four oleic acid concentrations, and subsequently, the mechanical and water barrier properties were evaluated. Enzyme concentration significantly affected mechanical and barrier properties of the films. Transglutaminase concentration at 1% improved tensile strength of control sample from 17.5 to 26.9 MPa while solubility decreased from 6.4% to 4.4%. Incorporation of oleic acid into transglutaminase‐treated zein films irrespective of enzyme concentration decreased water vapour permeability and solubility with the 1% transglutaminase‐treated zein films incorporated with 3% oleic acid registering the lowest permeability (0.37 g mm m^?2 h^?1 kPa^?1) and solubility (2.8%) values while elongation at break was not significantly improved. The use of transglutaminase at 1% concentration in cross‐linking zein films coupled with incorporation of controlled concentrations of oleic acid can be an effective approach in improving mechanical and water barrier properties of zein‐based films.