Effects of various plasticizers on mechanical and water vapor barrier properties of gelatin films

Different kinds of plasticizers were chosen to study the effects of plasticizer composition, size and shape on the mechanical properties and water vapor permeability (WVP) of gelatin films in this paper. Firstly, oligosaccharides – sucrose, and some organic acids such as oleic acid, citric acid, tartaric acid, malic acid (MA) were added to gelatin. It was found that only MA could improve the ductility of gelatin film, and the visual appearance of MA modified gelatin film was better. Secondly, polyethylene glycols (PEG) with different molecular weights (300, 400, 600, 800, 1500, 4000, 10?000, 20?000) were used to plasticize gelatin films. This showed that PEG of lower molecular weights exhibited better plasticizing effect for gelatin films, and such films had better visual properties. This shows that mannitol (Man) and sorbitol (Sor) could make gelatin films flexible, whereas Man could crystallize from gelatin film. Following this, the plasticization of ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG) series and ethanolamine (EA), diethanolamine (DEA), triethanolamine (TEA) series was studied. At last, suitable plasticizers (MA, PEG300, sorbitol, EG, DEG, TEG, EA, DEA, TEA) for gelatin were selected to investigate the WVP and water content of these plasticized gelatin films. The mechanical properties of these films were also compared.     

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.     

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.     

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.     

Mechanical and structural properties of rabbit skin gelatin films

In this article, the characteristics and structure of rabbit skin gelatin (RG) films were measured and compared with porcine skin gelatin (PG) films. The RG film was 8–10 μm thinner than that of PG film. RG films had better resistance to water and lower water solubility than did the PG film with the same gelatin and glycerol ratio due to the difference in their amino acid composition. The two types of gelatin films were almost transparent, which could give food a good appearance quality if these are used as packaging films. Both showed excellent barrier properties against UV light and could prevent the lipid oxidation reaction induced by ultraviolet light in the food system. The RG and PG films showed similar trends in mechanical properties as the change of their components. In general, the rigidity of the RG films was slightly lower than that of the PG films, but the flexibility was more prominent. This was due to intense interaction between gelatin molecules and glycerol molecules in RG films, but the dominant interaction was between the gelatin molecules in the PG films. The surfaces and cross-section microstructures of the RG and PG films were smooth and homogeneous, however for the RG films were more compact compared with the PG films.     

Mechanical properties and water vapor permeability of edible films made from fractionated soy proteins with ultrafiltration

Soy protein isolates (SPI) were fractionated by ultrafiltration unit equipped with 100 and 300 kDa cutoff size membranes. Glycerol-plasticized fractionated soy protein films were developed by casting methods. Mechanical, moisture barrier and physical properties of films, as affected by molecular weight of soy protein fraction, were investigated. Tensile strength and percent elongation at break of films increased with molecular weight of soy proteins. However, molecular weight variation did not influence the water vapor barrier properties of films. Protein solubilities of fractionated films were in the range of 3.5-4.6 g/100 g of dry film, whereas 11.9 g of proteins were solubilized from 100 g of dry SPI film. Hunter b value of fractionated protein films decreased with molecular weight of soy protein.     

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.     

Assessment of film-forming potential and properties of protein and polysaccharide-based biopolymer films

This study assessed the film‐forming abilities of six types of proteins, as well as six types of polysaccharides at various concentrations (proteins: 0–16%; polysaccharides: 0–4%) and heating temperatures (60–80 °C). Biopolymer films evaluated included: sodium caseinate (SC), whey protein isolate (WPI), gelatine (G); caboxymethyl cellulose (CMC), sodium alginate (SA) and potato starch (PS). Screening trials showed that optimal film‐forming conditions were achieved using SC and G (4% and 8%), WPI (8% and 12%), PS, CMC (2% and 3%) or SA (1% and 1.5%) solutions heated to 80 °C in combination with 50% (w/w) glycerol. Films manufactured from 1.5% SA, 8% G and 3% CMC had the highest tensile strength (24.88 MPa); flexibility (89.69%)/tear strength (0.30 N) and puncture resistance (22.66 N), respectively. SC, WPI and G‐based films were more resistant to solvent than SA, CMC and PS. Film permeability to water vapour and oxygen decreased in the order: 12% WPI to 1% SA and 12% WPI to 1% SA. All films tested were impermeable to oil.     

Effect of clay content, homogenization RPM, pH, and ultrasonication on mechanical and barrier properties of fish gelatin/montmorillonite nanocomposite films

The effect of clay content, homogenization RPM, and pH on the mechanical and barrier properties of fish gelatin/nanoclay composite films was investigated. The addition of 5% nanoclay (w/w) increased the tensile strength from 30.31 ± 2.37 MPa to 40.71 ± 3.30 MPa. The 9 g clay/100 g gelatin film exhibited the largest improvements in oxygen and water barrier properties. Oxygen permeability decreased from 402.8 × 10⁻⁶ ± 0.7 × 10⁻⁶ g m/m² day atm to 114.4 × 10⁻⁶ ± 16.2 × 10⁻⁶ g m/m² day atm and the water vapor permeability decreased from 31.2 × 10⁻³ ± 1.6 × 10⁻³ ng m/m² s Pa to 8.1 × 10⁻³ ± 0.1 × 10⁻³ ng m/m² s Pa. The XRD and TEM observation suggested that the ultrasonication treatment (30 min at 40% output) resulted in exfoliation of the silicates.     

Mechanical and water vapour barrier properties of edible gellan films

Edible films based on gellan were developed. Of the plasticizers tested, glycerol was found to be the most suitable with respect to mechanical properties and transparency. The mechanical properties (tensile and puncture), water vapour permeability (WVP) and glass transition temperature (T_g) were examined for gellan films as a function of glycerol concentration. The lowest effective glycerol concentration was ∼60% (film dry weight basis); below this concentration, the films tended to be brittle and difficult to handle, whereas films with more than ∼75% glycerol tended to be sticky. Addition of glycerol to gellan films increased extensibility (tensile elongation and puncture deformation) moderately, but decreased tensile strength, elastic modulus and T_g, and increased WVP of the films. Increasing the a_w caused marked decreases in tensile strength and elastic modulus, but decreased tensile elongation only slightly. In general, tensile strength and elastic modulus appeared to be more sensitive to changes in glycerol content and a_w than puncture strength.     

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.     

Conformational ordering and gelation of gelatin in mixtures with soluble polysaccharides

Previous studies have shown that conformationally disordered, soluble biopolymers cause large enhancements in self-association of calcium pectinate, thermally denatured whey protein and gelling maltodextrin under conditions where the pre-gel solutions remained as a single phase. The purpose of the present work was to screen for similar enhancements in gel strength and rate of conformational ordering of gelatin on incorporation of soluble, disordered polysaccharides. Type B gelatin was used at a fixed concentration of 5.0 wt%, at a pH well above its isoelectric point of ∼4.5. Mixtures were prepared at 45 °C, where the gelatin is in the disordered coil form. Gel strength was characterised as Young's modulus (E), derived from the initial slope of compression curves for gels formed by holding for 16 h at 5 °C. Rate of conformational ordering of gelatin (triple-helix formation) was monitored by changes in optical rotation during and after rapid quenching from 45 to 5 °C. The polysaccharides studied were carboxymethylcellulose (CMC), hydroxypropylmethylcellulose (HPMC), guar gum, gum arabic, dextran and inulin, all of which were used in compression testing. Combinations of gelatin with HPMC and guar gum became immediately turbid on mixing and could not, therefore, be included in the samples characterised by optical rotation. The other mixtures remained homogeneous (i.e. single-phase) on holding at 45 °C. The results obtained were entirely negative. Incorporation of the soluble polysaccharides caused no significant changes in Young's modulus, and optical rotation values remained within ∼10% of those for gelatin alone. It is suggested that the enthalpic advantage of segregation is sufficient to overcome the small reduction in entropy from association of conformationally immobile subunits in gelation of calcium pectinate, whey protein and maltodextrin, but not sufficient to overcome the much greater loss of entropy from conversion of flexible gelatin coils to rigid triple helices.     

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.     

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.     

An unusual manifestation of phase separation in mixtures of disordered gelatin with konjac glucomannan

The behaviour of konjac glucomannan (KGM) and the galactomannans locust bean gum (LBG), guar gum and fenugreek gum at a concentration of 0.2 wt% in mixtures with type B gelatin in the solution state at 40 °C was examined by visual inspection. At gelatin concentrations of ∼2 wt% and above, the mixtures with LBG and guar gum formed cloud-like flocs, attributed to association of unsubstituted “smooth” regions of the mannan backbone in response to segregative interactions with gelatin. Fenugreek gum, which has no such smooth regions, did not form flocs, but gave a dispersion of small, gel-like particles. Mixtures of gelatin with KGM showed the unusual, striking phenomenon of forming a single gel-like lump which remained suspended in the surrounding liquid, neither rising nor sinking. The single lumps formed by mixtures of 0.2 wt% KGM with 5.0 wt% gelatin were studied in detail. The gelatin content, as determined by macro-Kjedahl analysis and comparison of the area of differential scanning calorimetry (DSC) cooling and heating peaks with calibration curves for gelatin alone, was ∼1.35 wt%. Rheological characterisation by low-amplitude oscillatory measurements and creep-recovery experiments showed that, despite its gel-like appearance, the lump had the properties typical of a solution of densely entangled polysaccharide coils, including close Cox–Merz superposition of steady-shear viscosity (η) and complex dynamic viscosity (η*). The concentration of KGM, determined by comparison of the maximum value of η* in the Newtonian region at low frequency with calibration curves for KGM alone, was 3.4 wt%. The composition of the surrounding liquid was obtained by calculations of mass balance, giving values of 5.20 wt% gelatin and 0.024 wt% KGM. The “p-factor” determined as the ratio of water to gelatin in the solution divided by the ratio of water to KGM in the lump was 0.65, well within the range found for other biopolymer mixtures. It is concluded that the gelatin–KGM mixtures show normal liquid–liquid phase separation, but that the phases have exactly the same density, preventing resolution into two liquid layers, and that enthalpically unfavourable interactions are instead minimised by one of the phases assuming spherical geometry.     

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.     

Improvement of the antioxidant properties of squid skin gelatin films by the addition of hydrolysates from squid gelatin

Gelatin hydrolysates (HG1 and HG2) were obtained from giant squid (Dosidicus gigas) gelatins (G1 and G2) by hydrolysis with Alcalase. Antioxidant properties of both gelatins were highly increased by hydrolysis, especially ABTS radical scavenging capacity, whereas no significant differences were found between HG1 and HG2. The amino acid composition of HG1 and HG2 closely resembled the amino acid composition of the parent proteins, gelatins G1 and G2. Both, HG1 and HG2 were composed by peptides below 30 kDa, although no clear protein bands were observed in HG2. Edible gelatin films with increasing percentages of HG1 (0–10%) were made from G1, giving rise to increasing values of FRAP and ABTS, as well as changes in mechanical properties (decrease puncture force and increase puncture deformation) and water vapour permeability (increase). HG1 gelatin hydrolysate showed lower antioxidant capacity in the gelatin films than in the free form at the same amount added into the filmogenic solution, probably due to interactions with protein matrix.     

Thermomechanical properties of biodegradable films based on blends of gelatin and poly(vinyl alcohol)

The aim of this work was to study the effect of the poly(vinyl alcohol) (PVA) concentration on the thermal and viscoelastic properties of films based on blends of gelatin and PVA using differential scanning calorimetry (DSC) and dynamic-mechanical analysis (DMA). One glass transition was observed between 43 and 49 °C on the DSC curves obtained in the first scanning of the blended films, followed by fusion of the crystalline portion between 116 and 134 °C. However, the DMA results showed that only the films with 10% PVA had a single peak in the tan δ spectrum. However, when the PVA concentration was increased the dynamic mechanical spectra showed two peaks on the tan δ curves, indicating two T_gs. Despite this phase separation behavior the Gordon and Taylor model was successfully applied to correlate T_g as a function of film composition, thus determining k=7.47. In the DMA frequency tests, the DMA spectra showed that the storage modulus values decreased with increasing temperature. The master curves for the PVA–gelatin films were obtained applying the TTS principle (T_r=100 °C). The WLF model was thus applied allowing for the determination of the constants C₁ and C₂. The values of these constants increased with increasing PVA concentrations in the blend: C₁=49–66 and C₂=463–480. These values were used to calculate the fractional free volume of the films at the T_g and the thermal expansion coefficient of the films above the T_g.