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.     

Effect of some factors and pretreatment on the properties of porcine plasma protein-based films

The properties of porcine plasma protein-based films as influenced by some factors and pretreatment were studied. Both protein concentrations (20 and 30 g L⁻¹) and glycerol contents (50, 60 and 70 g/100 g protein) had the impact on film properties. Film prepared from film-forming solution (FFS) containing protein (30 g L⁻¹) and glycerol (60 g/100 g protein) possessed the highest tensile strength (TS) (2.48 MPa), while that containing protein (30 g L⁻¹) and glycerol (70 g/100 g protein) exhibited the greatest elongation at break (EAB) (18.33%). Protein and glycerol contents affected water vapor permeability (WVP) and transparency of the resulting films. No differences in protein solubility were found among all films (p > 0.05). Pretreatment of FFS by adjusting pH (2-11) and heating at different temperatures (40, 55 and 70 °C) on the properties of the resulting films was investigated. TS and EAB became higher but WVP decreased with decreasing or increasing pH value of FFS. Heat treatment of FFS with pH 3 and 10 had no impact on TS of the resulting film (p > 0.05). On the other hand, EAB and WVP increased with increasing temperature of FFS at both pHs (p < 0.05).     

Tensile, water vapor barrier and antimicrobial properties of PLA/nanoclay composite films

PLA-based composite films with different types of nanoclays, such as Cloisite Na⁺, Cloisite 30B and Cloisite 20A, were prepared using a solvent casting method and their tensile, water vapor barrier and antimicrobial properties were tested. Tensile strength (TS), elongation at break (E), and water vapor permeability (WVP) of control PLA film were 50.45 ± 0.75 MPa, 3.0 ± 0.1%, and 1.8 × 10⁻¹¹ g m/m² s Pa, respectively. TS and E of nanocomposite films prepared with 5 g of clay/100 g of PLA decreased 10-20% and 11-17%, respectively, depending on the clays used. On the contrary, WVP of the nanocomposite films decreased 6-33% through nanoclay compounding. Among the clay types used, Cloisite 20A was the most effective in improving the water vapor barrier property while sacrificing tensile properties the least. The effect of clay concentration tested using Cloisite 20A showed a significant decrease in TS and WVP, with increases in clay content. Among the PLA/clay composite films tested, only PLA/Cloisite 30B composite film showed a bacteriostatic function against Listeria monocytogenes.     

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.     

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.     

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.     

Properties and antioxidant activity of fish skin gelatin film incorporated with citrus essential oils

Properties of protein-based film from fish skin gelatin incorporated with different citrus essential oils, including bergamot, kaffir lime, lemon and lime (50% based on protein) in the presence of 20% and 30% glycerol were investigated. Films containing 20% glycerol had higher tensile strength (TS) but lower elongation at break (EAB), compared with those prepared with 30% glycerol, regardless of essential oils incorporated (p < 0.05). Films incorporated with essential oils, especially from lime, at both glycerol levels showed the lower TS but higher EAB than the control films (without incorporated essential oil) (p < 0.05). Water vapour permeability (WVP) of films containing essential oils was lower than that of control films for both glycerol levels (p < 0.05). Films with essential oils had varying ΔE^* (total colour difference), where the highest value was observed in that added with bergamot essential oil (p < 0.05). Higher glycerol content increased EAB and WVP but decreased TS of films. Fourier transforms infrared (FTIR) spectra indicated that films added with essential oils exhibited higher hydrophobicity with higher amplitude at wavenumber of 2874–2926 cm⁻¹ and 1731–1742 cm⁻¹ than control film. Film incorporated with essential oils exhibited slightly lower thermal degradation resistance, compared to the control film. Varying effect of essential oil on thermal degradation temperature and weight loss was noticeable, but all films prepared using 20% glycerol had higher thermal degradation temperature with lower weight loss, compared with those containing 30% glycerol. Films added with all types of essential oils had rough cross-section, compared with control films, irrespective of glycerol levels. However, smooth surface was observed in all film samples. Film incorporated with lemon essential oil showed the highest ABTS radical scavenging activity and ferric reducing antioxidant power (FRAP) (p < 0.05), while the other films had lower activity. Thus, the incorporation of different essential oils and glycerol levels directly affected the properties of gelatin-based film from fish skin.     

Physical and mechanical properties of water resistant sodium alginate films

Properties of sodium alginate films were modified using two different methods of CaCl₂ treatment, i.e. the direct addition of CaCl₂ into film making solution (mixing films) and the immersion of alginate films into CaCl₂ solutions (immersion films), and their treatment effects on tensile strength (TS), percentage elongation at break (E), water vapor permeability (WVP), and water solubility (WS) of the films were investigated. TS and E of the mixing films were not changed considerably, but those of the immersion films changed considerably with significant (P<0.05) increase in TS and decrease in E. WVP of the immersion films decreased significantly (P<0.05), but that of the mixing films did not decreased. Water resistance measured by WS was not improved with the mixing films, but the alginate films became water resistant when they treated by immersing in higher than 2 g/100 ml CaCl₂ solutions. Water adsorption by the films also decreased in the immersion films. Swelling ratio (SR) of the immersion film decreased with temperature without affecting WS of the films.     

Defatted mustard seed meal-based biopolymer film development

Edible films were developed from a defatted mustard seed meal (Sinapis alba) (DMM), a byproduct from the bio-fuel industry. Films were formed by casting DMM suspensions (3-g DMM/100-g suspension) that were treated by high-pressure homogenization (HPH, 138 MPa), ultrasound (400 W, 30 min), or gamma irradiation (10 or 20 kGy), and mixed with glycerol and soy lecithin. Rheological properties, water vapor permeability, water solubility, tensile strength (TS), percentage elongation (%E), elastic modulus (EM), color, and structural properties of film-forming suspensions or films were determined. Films were successfully produced using the HPH-processed suspension with 0.6% glycerol. Rheology results indicated the polymer network structure of the film-forming suspension was loosened by HPH, but tightened by heating at 90 °C. The ranges for the properties of WVP, WS, TS, %E, and EM of the films were 3.4-5.0 g mm/kPa h m², 30.3-34.4%, 1.3-5.5 MPa, 0.9-18.1%, 33.2-294.7 MPa, respectively. L, a, and b by CIELAB coordinates were 73.3-77.9, 0.4-3.5, and 29.5-45.7, respectively. HPH increased TS and %E of the films and decreased EM, whereas the ultrasound and the 20 kGy-irradiation treatments increased %E and decreased EM. The TS and EM decreased and E% increased with increasing glycerol and soy lecithin. DMM is a promising material to produce edible biopolymer films and coatings for food packaging.     

Properties of triticale flour protein based films

Triticale flour proteins based films were developed. Solubility in water, water vapor permeability (WVP), and mechanical properties of triticale films are presented. The effects of thermal treatments and glycerol concentration were also evaluated. WVP values were in the range 0.10-4.22 × 10⁻¹⁰ g m⁻¹ s⁻¹ Pa⁻¹. Tensile strength (TS) and percentage of elongation (%E) were in the range 2.9-0.20 MPa and 250-110% respectively. Total soluble matter (TSM), WVP, and %E decreased with the increase in the curing temperature. More plasticized films presented greater TSM, WVP, %E and lower values of TS. At a giving temperature (T) and glycerol concentration, an increase in relative humidity (RH) resulted in higher values of TSM, WVP, %E and lower TS values. It was observed that in films with the same treatments and conditioning, WVP increased with the increase in measurement temperature. Triticale proteins showed suitable film-forming capacity for the formulation of biodegradable films.     

Physical properties of a composite film containing sunflower seed meal protein and its application in packaging smoked duck meat

Sunflower seed meal protein (SP) films were prepared using various plasticizers, cross-linking agents, Cloisite Na⁺ or red algae, and their physical properties, such as tensile strength (TS), elongation at break (E), and water vapor permeability (WVP) were determined. The TS, E, and WVP of the SP film containing sucrose and fructose (2:1) as a plasticizer and cinnamaldehyde as a cross-linking agent were 3.05 MPa, 34.42%, and 2.25 × 10⁻⁹ g m/m² s Pa, respectively. The incorporation of Cloisite Na⁺ improved the physical properties of the SP film. The TS of the SP/Cloisite Na⁺ composite film containing 3% Cloisite Na⁺ increased by 2.19 MPa, and the WVP of the composite film decreased by 0.52 × 10⁻⁹ g m/m² s Pa compared to the SP film. The incorporation of red algae also improved the TS of the SP film. The TS of the SP composite film containing 1.2% red algae increased by 3.82 MPa compared to the SP film. In addition, an SP/red algae composite film containing grapefruit seed extract (GSE) was prepared and used in food packaging. After 12 days of storage, the population of Listeria monocytogenes inoculated on smoked duck meats packed with the SP/red algae composite film containing 1.2% GSE decreased by 1.31 log CFU/g compared to the control packaging. Therefore, these results suggest that SP composite films can be prepared by the addition of red algae to the SP film–forming solution and that the SP/red algae composite film containing GSE can be used as an antimicrobial food packaging material.     

Effect of flaxseed meal on the dynamic mechanical properties of starch-based films

Starch (S)–flaxseed meal (FM) biofilms were prepared from potato and maize starch by incorporating FM up to 15% (dry solid basis) and using glycerol as plasticizer. The dynamic mechanical properties, tensile properties and water vapor permeability (WVP) of these films were measured. The storage modulus of both the starch (control) and starch–FM films decreased as temperature increased. Tan δ increased initially in all the films with increase in temperature until a peak value was reached which allowed the determination of glass transition temperature (T_g). Both tensile strength and Young’s modulus of the starch–FM films increased with increase in the FM content. The WVP of the potato starch–FM films first increased to 2.261 (×10⁵ g m⁻² h⁻¹ Pa⁻¹) when FM content increased to 5% and decreased down to 1.832 (×10⁵ g m⁻² h⁻¹ Pa⁻¹) with further increase in the FM content to 15%. While the WVP values of the cornstarch and corn starch–FM films were not significantly (p > 0.05) different. The incorporation of FM increased the tensile strength, decreased the % elongation at break and increased the T_g.     

Development of fish gelatin edible films using extrusion and compression molding

Fish gelatin was plasticized with 20% and 25% glycerol (w/w of gelatin) and used to develop edible films by twin-screw extrusion at 110 and 120 °C followed by compression molding at 80 °C. Tensile and moisture barrier properties and glass transition temperature were then measured and compared with solution-cast films. The films extruded at 110 °C and with 25% glycerol had the highest percent elongation at break of 293 ± 27%. The water vapor permeability values of extruded films (the highest value being 2.9 ± 0.2 g mm h⁻¹ cm⁻² Pa⁻¹) were higher than those of solution-cast films while the glass transition temperatures (T_g) of the extruded films were generally lower than those of solution-cast films. Films with 25% glycerol that were extruded at 110 °C had the lowest T_g (2.10 ± 0.31 °C). This investigation showed that extrusion processing followed by compression molding is a feasible method to produce fish gelatin films for commercial applications in a wide range of food products.     

Roles of lipid oxidation and pH on properties and yellow discolouration during storage of film from red tilapia (Oreochromis niloticus) muscle protein

Protein-based films prepared from red tilapia (Oreochromis niloticus) washed and unwashed mince solubilised at pH 3 and 11 were prepared and characterised. Tensile strength (TS) of films from washed mince was greater than that of films prepared from unwashed mince for both pH used (P < 0.05). TS of films prepared at pH 3 was higher than that of films prepared at pH 11 for both of washed and unwashed mince (P < 0.05). Film from washed mince with pH 3 showed the highest TS, while that from unwashed mince with pH 11 had the lowest TS with the highest elongation at break (EAB) (P < 0.05). Films from washed mince had the lower value of thiobarbituric acid reactive substances (TBARS) than did those from unwashed counterpart, regardless of pH used. Nevertheless, TBARS was much higher in films prepared at acidic pH, compared with those prepared at alkaline pH. During storage of 20 days at room temperature, films became yellowish as evidenced by the increases in b^∗ and ΔE^∗-values. Films prepared at pH 11 showed the higher b^∗ and ΔE^∗-values than did those prepared at pH 3, especially for those from unwashed mince. However, films prepared from washed mince at pH 3 showed higher b^∗ and ΔE^∗-values than did those prepared at pH 11 (P < 0.05). Films generally had the increase in TS but the decreases in water vapour permeability (WVP), film solubility and protein solubility after 20 days of storage (P < 0.05). Therefore, lipid oxidation more likely played a role in yellow discolouration of fish muscle protein film, mainly by providing the carbonyl groups involved in Maillard reaction, while pH regulated the rate of reaction.     

Effects of plasticizers and nano-clay content on the physical properties of chicken feather protein composite films

To prepare chicken feather protein (CFP)/nano-clay composite films and to evaluate the effects of various plasticizers and nano-clay concentrations on the mechanical properties of the films, CFP composite films with various concentrations of Cloisite Na⁺ were prepared, and their physical properties such as tensile strength (TS), elongation at break (E), and water vapor permeability (WVP) were investigated. Optimal CFP films were formed with 5 g of CFP, 0.5 g of glycerol, and 1.5 g of sorbitol in 100 mL of film-forming solution; the TS, E, and WVP of the film were 4.74 MPa, 10.08%, and 3.11 × 10⁻⁹ g m/m² s Pa, respectively. After the nano-clay was incorporated into the CFP film-forming solution, scanning electron microscopy and X-ray diffraction studies were conducted to examine the structural characteristics of the CFP/nano-clay composite films. The incorporation of nano-clay improved the physical properties of the CFP films. The TS of the CFP/nano-clay composite film containing 7% Cloisite Na⁺ increased by 1.21 MPa, and the WVP of the composite film decreased by 1.15 × 10⁻⁹ g m/m² s Pa compared to the CFP film. Therefore, these results suggest that CFP composite films can be prepared with improved mechanical property by the addition of nano-clay and used as a food packaging material in the food industry.     

Mechanical and barrier properties of biodegradable soy protein isolate-based films coated with polylactic acid

Polylactic acid (PLA)-coated soy protein isolate (SPI) films were prepared by dipping SPI film into PLA solution. The effects of coating on improvements in mechanical and water barrier properties of the film were tested by measuring selected film properties such as tensile strength (TS), elongation at break (E), water vapor permeability (WVP), and water solubility (WS). TS of SPI films increased from 2.8±0.3 up to 17.4±2.1 MPa, depending on the PLA concentration of the coating solution, without sacrificing the film's extensibility. In contrast, the extensibility of SPI film coated with solution containing more than 2 g PLA/100 ml solvent, increased. WVP of PLA-coated SPI films decreased from 20 to 60 fold, depending on the concentration of PLA coating solution. Water resistance of SPI films was greatly improved as demonstrated by the dramatic decrease in WS for PLA-coated films. The improvement in water barrier properties was mainly attributed to the hydrophobicity of PLA.     

Structure-modifying alkaline and acidic pH-shifting processes promote film formation of soy proteins

The effect of pH-shifting, a process that induces the molten globule state in proteins, on the film-forming potential of soy protein isolate (SPI) at different temperatures was investigated. Partial unfolding at pH 1.5 or 12, followed by refolding at pH 7.0, was performed to alter the protein structure. Glycerin-plasticised films were prepared from pH-treated SPI at ambient temperature (20 °C), or by heating at 50, 60, 70, or 80 °C (30 min). Tensile strength (TS), elongation at break (EAB), water vapour permeability (WVP), protein solubility (pH 3–7), and non-participating proteins of films were analysed, and the film microstructures were examined. The pH₁₂-treated SPI spontaneously formed a transparent, slightly yellowish film at 20 °C, which had the greatest EAB, while pH_1.5-treated and native SPIs required preheating at 50 and 70 °C, respectively, to form a film. Heating generally decreased solubility and WVP but increased TS. Films formed from both pH₁₂- and pH_1.5-treated SPIs were more elastic (up to 2-fold greater in EAB, P < 0.05) than the film formed from untreated SPI despite slightly reduced TS and WVP. Electrophoresis revealed disulphide bonds between A and B subunits of glycinin being a dominant force in pH₁₂- and pH_1.5-treated SPI films, while noncovalent forces were abundant in untreated SPI films. The pH₁₂-treated SPI film consisted of more interactive protein strands than other SPI films, which seemed to explain its superior elastic properties.     

Manufacture and characterization of gelatin films derived from beef,pork and fish sources using twin screw extrusion

Gelatin films derived from beef, pork and fish sources were manufactured by twin-screw, co-rotating extrusion. The effect of extrusion processing parameters, namely; screw speed (100–400 rpm) and temperature (90, 90, 90, 90 °C and 90, 120, 90, 90 °C) on the mechanical and barrier properties of gelatin films were studied. Increasing screw speed up to 300 rpm improved (P < 0.05) tensile strength (TS) and reduced (non-significantly) water vapour permeability (WVP) values for all manufactured gelatin films. However, the WVP of various gelatin film types was reduced (P < 0.05) when a screw speed of 400 rpm was employed. Increasing the speed of extrusion promoted (P < 0.05) increased solubility of films in water. Manufacture of films using a higher temperature profile resulted in films possessing higher puncture strengths (PS), increased water barrier properties with higher water solubility.     

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.     

Effects of hydrogen peroxide and Fenton’s reagent on the properties of film from cuttlefish (Sepia pharaonis) skin gelatin

Properties of film from cuttlefish (Sepia pharaonis) ventral skin gelatin without and with partial hydrolysis (1.2% degree of hydrolysis), as influenced by H₂O₂ and Fenton’s reagent at different levels, were investigated. Films treated with H₂O₂ (0.01–0.04 M) and Fenton’s reagent [H₂O₂ (0.01–0.04 M) + FeSO₄ (0.001–0.004 M)] had higher tensile strengths (TS) but similar or lower elongations at break (EAB), compared with the control film (p < 0.05). Slight differences in water vapour permeability (WVP) were observed for all films. Films treated with Fenton’s reagent had a lower L^∗-value but higher a^∗-, b^∗- and ΔE^∗-values, while films treated with H₂O₂ had lower b^∗-values (p < 0.05), than had the control film. Cross-linking was pronounced in films treated with H₂O₂ or Fenton’s reagent and was associated with increased heat stability. Films treated with Fenton’s reagent had the lowest solubility in water (p < 0.05). However, fragmentation more likely took place when Fenton’s reagent (at a higher level) was used. Generally, similar results were noticeable between films from gelatin with and without partial hydrolysis. Thus, H₂O₂ and Fenton’s reagent directly affected the properties of film from cuttlefish skin gelatin, regardless of hydrolysis.