Preparation and characterization of agar/clay nanocomposite films: the effect of clay type

Abstract: Agar‐based nanocomposite 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 agar film were 29.7 ± 1.7 MPa, 45.3 ± 9.6%, and (2.22 ± 0.19) × 10^?9 g·m/m²·s·Pa, respectively. All the film properties tested, including transmittance, tensile properties, WVP, and X‐ray diffraction patterns, indicated that Cloisite Na⁺ was the most compatible with agar matrix. TS of the nanocomposite films prepared with 5% Cloisite Na⁺ increased by 18%, while WVP of the nanocomposite films decreased by 24% through nanoclay compounding. Among the agar/clay nanocomposite films tested, only agar/Cloisite 30B nanocomposite film showed a bacteriostatic function against Listeria monocytogenes.     

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.     

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.     

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 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 PLA lamination on performance characteristics of agar/κ-carrageenan/clay bio-nanocomposite film

Multilayer films composed of PLA and agar/κ-carrageenan/clay (Cloisite® Na⁺) nanocomposite films were prepared, and the effect of lamination of PLA layers on the performance properties such as optical, mechanical, gas barrier, water resistance, and thermal stability properties was determined. The tensile strength (TS) of the agar/κ-carrageenan/clay nanocomposite films (67.8 ± 2.1 MPa) was greater than that of PLA films (43.3 ± 3.6 MPa), and the water vapor permeability (WVP), water uptake ratio (WUR), and water solubility (WS) of the nanocomposite films were higher than those of PLA films. The film properties of the multilayer films exhibited better properties of the component film layers. Especially, the WVP and water resistance of the bionanocomposite film were improved significantly, while the OTR of the PLA film decreased profoundly after lamination with PLA layers. Thermal stability of the bionanocomposite also increased after lamination with PLA layers.     

Development and characterization of a novel biodegradable edible film obtained from psyllium seed (Plantago ovata Forsk)

In this study, the physical, thermal and mechanical properties of a novel edible film based on psyllium hydrocolloid (PH) were investigated. PH films were prepared by incorporation of three levels of glycerol (15%, 25%, and 35% w/w). As glycerol concentration increased, water vapor permeability (WVP), percent of elongation (E%) and water solubility of PH films increased whilst, tensile strength (TS), surface hydrophobicity and glass transition point (T_g) decreased significantly. At the level of 15% (W/W) of glycerol, PH films showed the lowest WVP values (1.16 × 10⁻¹⁰ g H₂O m⁻² s⁻¹ MPa⁻¹), E% (24.57%) and water solubility (47.69%) and the highest values for TS (14.31 MPa), water contact angle (84.47°) and T_g (175.2 °C). By increasing glycerol concentration, PH films became slightly greenish and yellowish in color but still transparent in appearance. This study revealed that the psyllium hydrocolloid had a good potential to be used in producing edible films with interesting specifications.     

Effect of clay content on the physical and antimicrobial properties of whey protein isolate/organo-clay composite films

Whey protein isolate (WPI)/Cloisite 30B organo-clay composite films with different amounts of the clay (0, 5, 10, and 20 g/100 g WPI) were prepared using a solution casting method and their properties were determined to assess the effects of clay content on film properties. The resulting films had an opaque appearance, which depended on the amount of clay added, and a similar gloss. However, the composite films were slightly less transparent compared to the transparent neat WPI films. Film properties, such as surface color and optical properties, varied depending on clay content. The haze index of the WPI/clay composite films as assessed by surface reflectance decreased indicating that the surface of the films was more smooth and homogeneous. The tensile and water vapor barrier properties of the composite films were also influenced by the amount of incorporated clay. In addition, WPI/Cloisite 30B composite films showed a beneficially bacteriostatic effect against Listeria monocytogenes.     

Effects of nanoclay type on the physical and antimicrobial properties of PVOH-based nanocomposite films

Polyvinyl alcohols-based nanocomposite films with four types of montmorillonite (MMT) nanoclay, including 18-amino stearic acid (I.24TL), methyl, bis hydroxyethyl, octadecyl ammonium (I.34TCN), di-methyl, di-hydrogenated tallow ammonium/siloxane (I.44PSS) organically modified MMT and a natural MMT (Na⁺-MMT) were fabricated by a solution-intercalation, film-casting method, and effects of the nanoclays were evaluated on physical properties, including transmittance, tensile strength (TS), elongation at break (E), water solubility (WS), swelling ratio (SR), water vapor uptake ratio (WVUR), and water vapor permeability (WVP), as well as antimicrobial activity of the polyvinyl alcohols-based films. Transmittance, WS, SR, WVUR, WVP of the nanocomposite films were significantly reduced by nano-composition compared to a pure polyvinyl alcohols film. The WVP decreased by 11.8–20.7%, and WS, SR and WVUR decreased by 19.9–41.8%, 9.1–26.4%, and 4.8–12.8%, respectively. The extent of changes was dependent on nanoclay type. X-ray diffraction patterns revealed that intercalation was formed in nanocomposite films. Overall among all the tested nanoclays, Na⁺-MMT showed more impact on physical properties of polyvinyl alcohols films, and the polyvinyl alcohols film compounded with quaternary ammonium group displayed remarkable antimicrobial activity against Gram-positive bacteria.     

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.     

Effects of nano‐clay type and content on the physical properties of sesame seed meal protein composite films

Sesame seed meal protein (SSMP)/nano‐clay composite films were prepared, and the physical properties of the films were determined. The SSMP film was prepared with 5 g of SSMP and 2 g of glycerol in 100 mL of film‐forming solution, and the tensile strength (TS), elongation (E) and water vapour permeability (WVP) of the SSMP film were 2.51 MP, 21.84% and 3.23 × 10^?9 g m m^?2s^?1 Pa^?1, respectively. Two types of nano‐clays were incorporated to enhance the physical properties of the SSMP film. The TSs of the SSMP film with 5% Cloisite Na⁺ and 7% Cloisite 10A were 6.32 and 5.76 MPa, respectively, and the WVPs of the SSMP nanocomposite films were 2.04 × 10^?9 g m m^?2s^?1 Pa^?1 compared with the SSMP film without nano‐clay, which was 3.23 × 10^?9 g m m^?2s^?1 Pa^?1. Therefore, these results indicate that the SSMP nanocomposite film can be applied in food packaging.     

Physical assessment of composite biodegradable films manufactured using whey protein isolate,gelatin and sodium alginate

Composite films were manufactured using whey protein isolate (WPI), gelatin (G) and sodium alginate (SA) using a simplex centroid design. Tensile strength (TS), puncture strength (PT), percentage elongation at break point (E), tear strength (TT), water vapour permeability (WVP) and oxygen permeability (OP) of films were evaluated. The interactions between biopolymers showed quadratic effects (P < 0.01) on TS, E, PT, TT and WVP values. Scanning electron microscopy (SEM) was performed to investigate the microstructures of composite films. The proportion of ingredients required to produce the optimum composite films was determined to be: WPI (g):G (g):SA (g) = 8.0:12.0:5.0. Overall, films (WPIGSA-9) produced using the combination of WPI (g):G (g):SA (g) = 10.0:16.0:14.0 demonstrated the best barrier to oxygen (8.00 cm³ μm/m² d kPa); while films (WPIGSA-1) showed the best barrier to water vapour (48.04 g mm/kPa d m²); films (WPIGSA-6) using the combination of WPI (g):G (g):SA (g) = 10.0:17.5:22.5 had the best mechanical properties of all of the experimental composite films tested.     

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).     

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.     

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 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.     

Characterization of antimicrobial polylactic acid based films

Olive leaf extract (OLE) (Olea europaea L.), which has antimicrobial effect on many food pathogens, was incorporated as antimicrobial agent into polylactic acid (PLA) films. Antimicrobial activities of films were tested against Staphylococcus aureus. Increasing amount of the OLE in the film discs from 0.9 mg to 5.4 mg caused a significant increase in inhibitory zones from 9.10 mm to 16.20 mm, respectively. Moreover, incorporation of OLE and/or increasing the amount in the film formulation significantly enhanced the water vapor permeability (WVP). The water solubility and the degradation rates of films increased up to 19.3% and 22.4%, respectively. Thus, OLE incorporated PLA films have a prospectively potential in antimicrobial food packaging to reduce post-process growth of S. aureus with improved properties.     

Properties of Bio-nanocomposite Films from Tilapia Skin Gelatin as Affected by Different Nanoclays and Homogenising Conditions

Fish gelatin films incorporated with hydrophilic and hydrophobic montmorillonite (mmt) nanoclays with the aid of homogenisation using different pressure levels (1,000 to 4,000 lb/in²) and passes (two and four) were characterised. Young’s Modulus, tensile strength and elongation at break of films decreased with increasing pressure levels and number of passes. High pressure homogenisation generally lowered the mechanical properties of nanocomposite films. Additionally, water vapour barrier property became poorer, when high pressure homogenisation was implemented. Films incorporated with hydrophobic nanoclay (Cloisite 20A) exhibited the lower water vapour permeability (WVP) than those with hydrophilic nanoclay (Cloisite Na⁺). Colour parameters (L*, a*, b* and ?E*) of nanocomposite films were affected to some degrees by homogenisation conditions. Transparency of films increased when homogenisation pressure and number of passes increased. As revealed by wide angle X-ray diffraction (WAXD) analysis, nanocomposite films prepared using homogenisation had exfoliated nanostructure, whilst those prepared without homogenisation exhibited intercalated nanostructure. Thermogravimetric (TGA) and differential scanning calorimetric (DSC) analyses indicated that thermal stability of nanocomposite films varied with homogenisation condition, being higher in these films than in those without nanoclay. Thus, homogenisation condition and hydrophobicity of nanoclay directly affected the properties of nanocomposite films from fish skin gelatin.     

Physical and antimicrobial properties of Gelidium corneum/nano-clay composite film containing grapefruit seed extract or thymol

To improve the physical properties of Gelidium corneum (GC) film, Cloisite Na⁺ and 30B were incorporated into the preparation of the film. X-ray diffraction patterns of the films indicated that a degree of exfoliation and intercalation are formed depending on the type of nano-clays and its concentration and the film structure affects the physical properties of the GC/nano-composite films. Tensile strength (TS) of the GC film was increased by the addition of nano-clays. GC film had a TS of 19.59 MPa for the control, while the GC film having 3% Cloisite Na⁺ or 30B had TS of 27.37 and 26.40 MPa, respectively. Elongation at break and water vapor permeability were also improved by the addition of 3% nano-clays. The physical properties of the film were not improved by the addition of GSE or thymol, but the additions did inhibit the growth of Escherichia coli O157:H7 and Listeria monocytogenes. The results suggest that the nano-composite films containing GSE or thymol may extend the shelf life of food.     

Properties of film from cuttlefish (Sepia pharaonis) skin gelatin incorporated with cinnamon,clove and star anise extracts

Properties of film from cuttlefish (Sepia pharaonis) ventral skin gelatin without and with partial hydrolysis (1.2% degree of hydrolysis) incorporated with 1% ethanolic extract of cinnamon (CME), clove (CLE) and star anise (SAE) were determined. Films with different herb extracts (without and with oxidation) had higher tensile strength (TS) but lower elongation at break (EAB), compared with the control film (without addition of herb extracts) (p < 0.05). Lower water vapor permeability (WVP) and L^∗-value but higher b^∗- and ΔE^∗-values were observed when the extracts were incorporated (p < 0.05). Electrophoretic study revealed that cross-linking was pronounced in films containing different herb extracts. Oxidized extracts yielded films with higher TS and WVP than those without oxidized herb extracts (p < 0.05). Generally, similar properties were noticeable for films from gelatin with and without partial hydrolysis. Nevertheless, higher mechanical properties were obtained for the latter. FTIR spectra indicated that protein–polyphenol interactions were involved in the film. Thermo-gravimetric analysis revealed that films incorporated with SAE or SAE with oxidation (OSAE) exhibited lower heat susceptibility and weight loss in the temperature range of 50–600 °C, compared with control film. Films with SAE and OSAE had smoother surface for gelatin without hydrolysis; however, coarser surface was observed in film from gelatin with partial hydrolysis. Thus, the incorporation of different herb extracts directly affected the properties of film from cuttlefish skin gelatin with and without hydrolysis.