International Journal of Food Science and Technology 2006, 41, 295–302 Original article Effect of food ingredients and selected lipids on the physical properties of extruded edible films/casings Li Liu, John F. Kerry & Joe P. Kerry* Department of Food and Nutritional Sciences, University College Cork, Cork, Ireland (Received 14 December 2004; Accepted in revised form 29 April 2005) Summary Films/casings produced using pectin (PN) and gelatin/sodium alginate blends (GSAB) containing 2.5 and 5% added corn oil (CO) or olive oil (OO) and non-oil containing were manufactured using extrusion technology. Films/casings formed from PN and GSAB had great difference in properties of tensile strength, elongation, Young’s modulus and puncture resistance. Quality and stability of films/casings were greatly enhanced on addition of oils. However, an oil addition of 2.5% was identified as optimal while 5% decreased the final films/casings quality. Oil addition increased (P < 0.05) films/casings thicknesses. Oil addition also decreased (P < 0.05) tensile strength, puncture resistance, Young’s modulus and tear resistance of films/casings but increased their elongation properties, with the exception of converse effect of 2.5% CO on two films/casings. Olive oil and CO both reduced (P < 0.05) water vapour transfer rate (WVTR) of films/casings. However, no significant difference between films using different concentrations of oil was observed with respect to WVTR. Keywords Edible films/casings, extrusion, mechanical properties, water barrier properties. Introduction Interest in the development of edible films and coatings has increased in recent years because of their potential to improve the quality and stability of wide range of food products (Baldwin et al., 1997; Cuq et al., 1998; Debeaufort et al., 1998). A range of processing methods suitable for the fabrication of edible films and coatings including; plate casting, spraying, dipping, etc. have been reported (Donhowe & Fennema, 1994). Successful application of extrusion technology in the manufacture of stable edible films merits further investigation because of its ability to manipulate food polymer structure and functionality (Liu et al., 2004). Different materials could form films with different properties, for example, polysaccharides and proteins have been proved to be able to form strong films but possess poor water vapour barrier *Correspondent: Fax: 00-353-4270213; e-mail: [email protected] doi:10.1111/j.1365-2621.2005.01063.x 2005 Institute of Food Science and Technology Trust Fund properties. However, most single hydrophobic films or coatings (made from lipids) while possessing high water barrier properties, form brittle films. However, moisture barrier properties of hydrophilic films can be improved through the incorporation of hydrophobic materials such as waxes, long-chain saturated fatty acids, or through emulsion or lamination technology (Fennema et al., 1994; Handa et al., 1999; Garcia et al., 2000). Thus, composite films and casings can be manipulated to combine the advantages of both lipid and hydrocolloid components (Kester & Fennema, 1989b; Krochta & Johnson, 1997). Lipid addition during film and casing formulation can serve as an effective barrier to water vapour while the hydrocolloid component can impart both oxygen and carbon dioxide barrier properties, as well as form the necessary supporting matrix of the film or casing (Wong et al., 1994; Baldwin et al., 1997; Garcia et al., 2000). The water vapour transfer through films and casings generally occurs via the hydrophilic 295 296 Effect of food ingredients and selected lipids L. Liu et al. portion within the system, with the water vapour permeability (WVP) dependent upon the hydrophilic–hydrophobic ratio of the matrix components (Hernandez, 1994). WVP increases with polarity, unsaturation, lipid branching/structure and is further dependent upon the water absorption properties of the polar components of the film or casing (Gontard et al., 1994; Garcia et al., 2000). Barrier and mechanical properties depend on film microstructure, which in turn can influence the films composition, formation and method of product containment (Cuq et al., 1995). Further studies have also shown that when lipids are employed as laminating agents or within a hydrophilic film and form a bilayer or emulsified to form a composite emulsion, the barrier against water vapour transfer were both improved. Studies, where long-chain fatty acids and solid lipids were utilized in the preparation of composite films, were shown to possess an effective water vapour resistance (Kamper & Fennema, 1984; Kester & Fennema, 1989a). Other than reports on manufacturing patents for the production of edible/biodegradable extruded casings (Lieberman, 1967; Shank & Shank, 1972), little research appears to be available in the current scientific literature relating to this form of packaging material, and in particular, on the use of food grade oils in the formation of extruded edible films/casings. The objectives of this study were to generate test composite edible films/casings utilizing an emulsified solution containing oils and food polymers using extrusion technologies previously reported (Liu et al., 2004), and to evaluate appearance, mechanical properties and WVPs of extruded test films/casings containing different food ingredient substrates. The effects of addition of different oils fractions on properties above against non-oil containing controls were also carried out. Materials and methods Food ingredients The following materials were used in this study: sodium alginate (Manucol DM; International Specialty Products HQ, Tadworth, UK); gelatin (bloom 264, Klippan, Sweden); high methoxy pectin (CP Kelco, Lille Skensved, Denmark), glycerol and lecithin (Sigma Chemical Company, St Louis, MO, USA), corn oil (CO) (Mazola) and olive oil (OO) (Don Carlos) were purchased from Pallas Foods, Limerick, Ireland. Film/casing manufacture All films/casings were formed according to the methods outlined by Liu et al. (2004) with the exception of 2.5 and 5% OO and CO being incorporated into the mixture of water, glycerol and 1% lecithin for emulsification purposes. The composition of each film/casing generated in this study is shown in Table 1. Some casings were cut on one side of the die after extrusion, thus allowing for the formation of a continuous strip of film. The remaining films/ casings were stored for additional tests. All test Table 1 Film/casing composition Composition Lipid (%) Film/casing types Protein (%) Carbohydrate (%) Water (%) Glycerol Oil PN without oil GSAB without oil PN with 2.5% CO PN with 5% CO GSAB with 2.5% CO GSAB with 5% CO PN with 2.5% OO PN with 5% OO GSAB with 2.5% OO GSAB with 5% OO 0 7.82 0 0 7.82 7.82 0 0 7.82 7.82 54.14 31.26 54.14 54.14 31.26 31.26 54.14 54.14 31.26 31.26 22.93 30.46 21.79 20.64 28.94 27.42 21.79 20.64 28.94 27.42 22.93 30.46 22.93 22.93 30.46 30.46 22.93 22.93 30.46 30.46 0 0 1.15 2.29 1.52 3.05 1.15 2.29 1.52 3.05 International Journal of Food Science and Technology 2006, 41, 295–302 2005 Institute of Food Science and Technology Trust Fund Effect of food ingredients and selected lipids L. Liu et al. films/casings were placed in a drying room at 23 ± 2 C (50% ± 5% RH) for 3 days. three independent samples, from each film/casing type was used to establish permeability values. Appearance evaluation of extruded casings Statistical analysis Appearances of films/casings manufactured both with and without oil were assessed after 3 days storage in drying chamber. Film/casing samples were then transferred to a chill (4 C) room and displayed for 2 days to evaluate practical environmental effects on films/casings appearance. Data were analysed by one-way analysis of variance, using SPSS software (version 11.0; SPSS, Dublin, Ireland). Post hoc multiple comparisons were determined by least significant difference (LSD). All comparisons were made at a 5% level of significance. Film thickness and mechanical properties Results and discussion Film thickness and mechanical properties were measured using the methodologies described by Liu et al. (2004). Water vapour transfer rate (WVTR) of films/ casings Water vapour transfer rate of films was measured using WPA-100 (VTI Corporation, Hialeah, FL, USA). Three samples with a surface area over 6.8 cm2 were taken from each film/casing. Each sample was then attached to an adhesive mask (to prevent the film/casing being damaged during the test) which had a circular hole of 6.8 cm2 in the centre, over which the film was placed. The mask with the test film/casing sample was mounted onto instrumental cylinders, followed by analysis. Instrumental operating parameters were: 23 ± 2 C temperature, 50 ± 5% relative humidity (RH), 500 cc min flow rate and 0.005 WVTR in 5 min equilibrium. The reading obtained was the WVTR value for that sample. The average value of Appearance assessment Both pectin (PN) and gelatin/sodium alginate blend (GSAB) without oil formed stable films/ casings (Table 2). However, after holding test films/casings under refrigerated conditions, samples quickly absorbed moisture, expanded, became weak and split. Addition of oil to film/casing formulations containing PN resulted in very stable packaging materials. Upon refrigerated storage, PN based films/casings were stable, remained intact and had higher flexibility compared with similar films/ casings formed without the use of oil. Therefore, oil addition successfully reduced water absorption by PN-based films/casings, thereby, improving extruded film/casing properties. However, addition of 5% CO or OO to PN formulations reduced film/casing strength compared with those manufactured using concentration of 2.5% oil. Both 2.5% CO and OO improved the overall quality of films/casings containing GSAB. Films/ Table 2 Description of appearances of films/casings formed from PN and GSAB Films/casings types Appearances of films/casings following chilled storage PN without oil GSAB without oil PN with 2.5% CO PN with 5% CO GSAB with 2.5% CO GSAB with 5% CO PN with 2.5% OO PN with 5% OO GSAB with 2.5% OO GSAB with 5% OO Casings became wet, suffered from cracking and broke easily on handling Casings became wet, suffered from cracking and, broke easily on handling Casings became wet but were soft and flexible with good integrity Casings became wet and slightly brittle but were soft and flexible with moderate integrity Casings became wet but were soft and flexible with good integrity Did not form acceptable casings Casings became wet but were soft and flexible with good integrity Casings became wet and slightly brittle but were soft and flexible with moderate integrity Casings became wet but were soft and flexible with good integrity Did not form acceptable casings 2005 Institute of Food Science and Technology Trust Fund International Journal of Food Science and Technology 2006, 41, 295–302 297 International Journal of Food Science and Technology 2006, 41, 295–302 4.21bcd 2.51cdef 2.91bc 1.17gh 1.24g 1.53cde 1.36a 2.63ab ± ± ± ± ± ± ± ± 0.04bcd 0.05bc 40.56 37.45 42.37 24.63 25.87 37.98 47.27 44.20 0.04a 0.02ab 0.01e 0.01ef 0.01efg 0.09 ± 0.07 ± 0.02 ± 0.02 ± 0.02 ± – 0.05 ± 0.06 ± 0.78a 0.20fg 0.40ab 0.39f 0.12h 0.48de 0.63d 0.25c ± ± ± ± ± ± ± ± 7.79 3.23 7.23 3.51 2.31 4.15 4.17 6.43 0.02a 0.01d 0.01de 0.01gh 0.01fg 0.01bc 0.05b 0.01f ± ± ± ± ± ± ± ± Values within rows followed by the same letter are not significantly different at P £ 0.05. 0.58 0.17 0.14 0.05 0.07 0.24 0.30 0.08 2.26fg 3.95fgh 5.31bc 8.58d 6.48de 9.59ab 5.38ef 5.55a ± ± ± ± ± ± ± ± 25.01 24.57 44.96 36.09 31.33 50.66 25.99 57.93 0.39a 0.27e 0.99b 0.49f 0.32fg 0.17fgh 1.16c 0.52cd ± ± ± ± ± ± ± ± 7.26 2.74 6.29 1.96 1.82 1.03 5.55 5.31 0.02bc 0.03a 0.02bcd 0.02b 0.02bcde 0.01bcdef 0.02g 0.01gh ± ± ± ± ± ± ± ± 0.51 0.57 0.51 0.52 0.51 0.50 0.36 0.36 PN with 2.5% CO PN with 5% CO GSAB with 2.5% CO PN with 2.5% OO PN with 5% OO GSAB with 2.5% OO PN without oil GSAB withou oil Tear resistance (kg) Puncture resistance (kg) Young’s modulus (MPa) Percentage of elongation (%) Tensile strength (MPa) No significant differences in thickness were observed between films/casings manufactured from PN and GSAB without the use of oil (Table 3). The thickness for films/casings using oil was higher (P < 0.05) than films manufactured without oil. The 5% CO PN film/casing had a higher (P < 0.05) thickness value than all other experimental films/casings manufactured with oil. Kester & Fennema (1986) and Greener & Fennema (1989) reported that edible films containing hydrophobic substances such as waxes and oils can form thicker films. The possible reasoning for this may be because of the water content present in lipid-emulsified films. Under similar ageing conditions, the amount of water evaporated from composite films ere less compared with that evaporated from films manufactured without lipids. Thickness (mm) Thickness values for films/casings Films casings manufactured with oil were stronger and less likely to tear or split than those manufactured without oil following storage at 4 C. While all films/casings were visually observed to swell because of increased water uptake during chilled storage, they maintained acceptable integrity and strength. Like PN, the use of a 5% oil concentration negatively affected the formation of stable GSAB films/casings, which showed that film/ casing formed from GSAB was less tolerant to high level oil (including CO and OO) compared with film/casing formed from PN. Water has been reported to be the most ubiquitous and uncontrollable plasticizer used in the manufacture of edible films and its presence decreases the mechanical strength of edible films (Gontard et al., 1993). Mechanical properties of edible/biodegradable films like tensile strength and puncture resistance have been shown to be negatively affected by environmental RH and film water content (Greener-Donhowe & Fennema, 1993; Debeaufort & Voilley, 1997). Findings reported in this study support the observations made by a number of researchers (Gontard et al., 1993; Debeaufort et al., 1998). However, results from this study also showed that the problems created by the unwanted presence of moisture in edible/ biodegradable films can be circumvented or prevented through the use of oil. WVP (g H2O/ day/100 in2) Effect of food ingredients and selected lipids L. Liu et al. Table 3 Properties of extruded films/casings formed from PN and GSAB both with and without oil 298 2005 Institute of Food Science and Technology Trust Fund Effect of food ingredients and selected lipids L. Liu et al. Mechanical properties of films/casings No significant difference in tensile strength was determined between films/casings manufactured from PN and GSAB without the use of oil. CO (2.5%) improved (P < 0.05) the tensile strength of both films/casings and also had higher (P < 0.05) tensile strength than other oil emulsified films/casings. PN films/casings with 5% CO also had higher (P < 0.05) tensile strength than films/casings containing OO. Elongation of film/casing of GSAB without oil was higher (P < 0.05) than that of film/casing formed from PN without oil. Elongation of PN films/casings was unaffected when CO was used while, 2.5% CO reduced (P < 0.05) elongation of films/casings manufactured using GSAB. Both 2.5 and 5% OO improved (P < 0.05) elongation properties of PN films/casings. OO reduced elongation properties of films/casings manufactured from GSAB. Film/casing of PN without oil had higher (P < 0.05) Young’s Modulus than film/casing of GSAN without oil. CO (2.5%) improved (P < 0.05) Young’s modulus of PN films/casings. The use of 5% CO and 2.5% and 5% OO reduced (P < 0.05) Young’s modulus values for PN films/ casings. Films/casings manufactured from GSAB using both CO and OO improved (P < 0.05) Young’s modulus values. Young’s modulus values for films/casings formed from PN using OO were lower (P < 0.05) than all other films. Film/casing based on PN without oil had lower puncture resistance (P < 0.05) compared with film/casing based on GSAB without oil. CO (2.5%) improved (P < 0.05) puncture resistance of both films/casings types to the same degree. However, the use of 5% CO, and 2.5% and 5% OO reduced (P < 0.05) puncture resistance of PN-based films/casings. OO (2.5%) decreased (P < 0.05) puncture resistances of films/casings formed from GSAB. No significant difference of tear resistance was found between films/casing formed from PN and GSAB without addition of oils. PN films/casings manufactured with 2.5 and 5% CO had higher (P < 0.05) tear resistances than controls without oil. Films/casings formed from PN with 2.5 and 5% OO and films/casings manufactured from GSAB with 2.5% CO had the similar tear 2005 Institute of Food Science and Technology Trust Fund resistance values. These values were lower (P < 0.05) than tear resistance values for films/ casings formed from PN and GSAB without oil. Composition of films/casings had great effect on film mechanical properties. Film/casing formed from PN had higher tensile strength, Young’s Modulus but lower elongation and puncture resistance compared with film/casing formed from GSAB. Debeaufort et al. (2000) reported that lipids strongly affected the mechanical properties of film when they were mixed to the hydrocolloid as an emulsion. Tensile strength (Banerjee & Chen, 1995; Gennadios et al., 1996) and puncture resistance (Gontard et al., 1994) decreased when lipid sources have been added to edible/biodegradable film formulations. According to Lai et al. (1997) and Gallo et al. (2000), the use of liquid lipids in films enhanced elongation properties since lipid oils produce lubrication in emulsified films, however, this in turn reduces other mechanical properties. In this study, OO similarly to those lipid sources cited above in extruded edible/biodegradable films such as decreased the tensile strength, puncture resistance and tear resistance for both PN and GSAB films/casings and increased the elongation of PN based films/casings. CO (5%) also had similar effects to OO in PN-based films. The reasons for the negative effects of lipids on mechanical properties of composite films were given by other researchers as the lack of selfsupporting and lubrication of lipids. Yang & Paulson (2000) even supposed that in composite films, the main ingredient polymer were partially replaced by lipid and the interaction between nonpolar lipid molecules and between polar polymer and no-polar lipid molecules are certainly much lower than those between the polar polymer molecules. Conversely, in this study, 2.5% CO was found to increase tensile strength, Young’s modulus and puncture resistance in both PN and GSAB films/ casings, but decreased elongation properties. This was totally different from most of other researches. According to Mor et al. (1999), protein matrix with dispersed lipid can be classified as two systems: interactive or non-interactive. In interactive system, lipid emulsified in protein matrix could be covered by protein and become an integrate part of the network. These oil globules International Journal of Food Science and Technology 2006, 41, 295–302 299 300 Effect of food ingredients and selected lipids L. Liu et al. fitted into the matrix and served as many anchor points that strengthened the whole network. Many other researchers (McClements et al., 1993; Line et al., 2004) also got the same finding to support this. Compared with protein emulsion system, the influence of lipid incorporation on mechanical properties of hydrocolloid systems has not been extensively investigated. However, it is reasonable to suppose that the similar principle exists in the hydrocolloid emulsion system, is that, lipid participated in the formation of the whole network of films. 2.5% CO under the condition in this work might be able to cooperate with matrix of PN and GSAB and became and integrate part of the whole films/casings, thereby, increased mechanical properties of these two extruded films/casings, with the exception of elongation. In this study, the effect of OO on elongation of the GSAB film was different from results previously shown in the scientific literature. Most studies assessing the effect of lipids on properties of films have concentrated on single ingredient films. The role of lipid in such kind of films is more defined and predictable, unlike that of composite films. Films/casings formed from GSAB without oil had very high value of elongation because of the existence of gelatin, which individually produced very soft and sticky extruded products, with high elasticity (unpublished work carried out in our laboratory). The use of gelatin introduced greater properties of elasticity and elongation and films/ casings manufactured using GSAB. The addition of OO may have counteracted the function of gelatin in this composite film/casing, thus reduced the elongation of films/casings formed from GSAB. Certainly, further investigations to clearly understand the effects of low-level CO on film mechanical properties and OO on elongation of films formed from GSAB are required. Water vapour transfer rate (WVTR) Film/casing formed from PN without oil had higher WVP compared with GSAB films/casings without oil, but the difference was not significant. Both CO and OO decreased (P < 0.05) the WVTR of PN films/casings. The use of OO lowered (P < 0.05) WVTR in PN films/casings compared with those manufactured with CO, regardless of oil concentration used. Only OO lowered (P < 0.05) the WVTR of films/casings manufactured from GSAB. The form of lipid added to edible films has been shown to have a pronounced effect on the WVP, the long chain and solid lipids producing greater barrier effects than the short chain and liquid lipids (Kamper & Fennema, 1984). This effect was hypothesized to be because of the increasing crosslinking at the film interface between the lipid layer and the hydrocolloid layer (McHugh & Krochta, 1994a). Interestingly, while OO used in this study had shorter fatty acid chains compared with CO, it produced more positive effects on the WVTR properties of extruded films. The reason for this difference may be because of the extrusion manufacturing process used. From extensive review of the literature, the majority of studies examining the effects of lipids on moisture barrier property of edible films have been conducted on films manufactured using the solution casting method. With this method, biopolymer solutions were heated using low temperature (normally 80 C). Compared with the casting films, extruded films/casings in this study were heated under much higher temperature (135 C) and certain pressure. The form and function of oil and their effects on moisture barrier property may have been affected and altered by higher heating temperature and pressure compared with those using lower heating temperature and without pressure. The details of this effect need to be studied and understood further. Besides the type of lipids used in the manufacture of edible/biodegradable films, the amount of lipid was also reported to be an important factor for the moisture barrier property of films, the greater the amount of lipid used, the lower the WVP (Shellhammer & Krochta, 1997). While limited by the scope of the extrusion technology used, no such concurring result was determined in this study. It is possible that because a lipid concentration not exceeding 5% was used in this study, range of oil concentrations was not wide enough to show the full effect of oil on WVTR of extruded films/casings. Acknowledgments This research was part funded by the Irish Department of Agriculture under the National International Journal of Food Science and Technology 2006, 41, 295–302 2005 Institute of Food Science and Technology Trust Fund Effect of food ingredients and selected lipids L. Liu et al. Development Plan through the FIRM Research Programme. 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