Journal of Food Engineering 109 (2012) 189201

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Journal of Food Engineering

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Comparative study of lm forming behaviour of low and high amylose starches using glycerol and xylitol as plasticizers
D. Muscat a, B. Adhikari a,, R. Adhikari b, D.S. Chaudhary c
a

School of Health Sciences, University of Ballarat, VIC 3353, Australia CSIRO Materials Science and Engineering, Clayton South, VIC 3169, Australia c Department of Chemical Engineering, Curtin University of Technology, Perth, WA 6102, Australia
b

a r t i c l e

i n f o

a b s t r a c t
In this study, the lm forming behaviour of low amylose (LA) and high amylose (HA) starches was studied. The starch-alone and a blend of plasticizer (polyol)starch lms were developed by gelatinising at various temperatures and casting at 25 C. The starchplasticizer lms contained glycerol and xylitol either individually or in 1:1 combination. The concentration of plasticizer used was 15%, 20% and 30% for LA lms while it was 20%, 30% and 40% for HA lms on dry solid basis. The HA-glycerol lms retained the highest moisture content among all the lms. The HA lms exhibited higher glass transition temperature, higher tensile strength, higher modulus of elasticity and lower elongation at break than those obtained from LA starch. The tensile strength and modulus of elasticity decreased and the elongation increased with increasing plasticizer concentrations above 15% on dry solid basis regardless the starch type. Low water vapour permeability was evident in LA and HA lms plasticized by combined plasticizers at 20% plasticizer concentration. Rheological measurements showed that most of the suspensions exhibited HerschelBulkley behaviour and some of the HA suspensions exhibited Bingham plastic behaviour. At 15% (on dry solid basis) plasticizer concentration, the lms obtained from both the starches were brittle due to the anti-plasticization behaviour. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 16 February 2011 Received in revised form 7 October 2011 Accepted 12 October 2011 Available online 19 October 2011 Keywords: High amylose Low amylose Corn starch Glycerol Xylitol Film Mechanical properties Water vapour permeability Anti-plasticization

1. Introduction We are literally wrapped in petroleum based plastics. These plastics are used as packaging material in almost every product we buy, most of the foods and drinks we consume. This is because they provide excellent protection for the product, are cheap to manufacture and are durable. However, they are not biodegradable due to their very large polymer molecules and stable carbon hydrogen bond, both of which make its decomposition by organisms rather difcult. The non-biodegradable and non-renewable nature of these plastics is major environmental concern. Because of the increased awareness in preserving the natural environment, efforts have been made to develop biodegradable plastics that are made from renewable resources, such as plants, which are compostable. Their characteristics include being hydrophilic, most can be processed directly; either plasticized, as llers or modied by chemical reactions. Such green changes in packaging will improve sustainability and reduce the adverse impact plastic packaging places on the environment because of their biodegradability (Yakimets et al., 2007).

Corresponding author. Tel.: +61 3 53279249; fax: +61 3 53279240.

E-mail address: b.adhikari@ballarat.edu.au (B. Adhikari). 0260-8774/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.jfoodeng.2011.10.019

Among the biopolymers investigated as potential alternative raw materials for plastics, starch has drawn a great deal of attention. The appeal of starch is that it is biodegradable, renewable, inexpensive and for the most part easily handled (Zhang and Han, 2006). However, starch itself has poor processability, dimensional stability and mechanical properties for its end products. Therefore, native starch cannot be used directly as packaging material (Lu et al., 2009). Starch is the most abundant storage glucan composed of two main structural components, amylose and amylopectin (Sajilata et al., 2006). Amylose is a linear molecule of glucose units linked with a-(1 ? 4) bonds. Amylopectin is a branched molecule with a-(1 ? 6)-linked branch points and linear regions of a-(1 ? 4)linked glucose units (Murphy, 2000). There are many hydroxyl groups on starch chains, two secondary hydroxyl groups at C-2 and C-3 of each glucose residue, as well as one primary hydroxyl group at C-6 when it is not linked because of which starch is hydrophilic material. The available hydroxyl groups on the starch chains participate in the formation of hydrogen bonds (Lu et al., 2009). In its native granular form starch has limited applications. To fully realise the starch biopolymers functionality, granule disruption and sometimes chemical modication are necessary. To produce biodegradable packaging, starches are rst gelatinised (Cooper et al., 2003). This process transforms the starch from a

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D. Muscat et al. / Journal of Food Engineering 109 (2012) 189201

crystalline granular into a rubbery paste with no structure at all. During gelatinisation several changes occur to the starchwater system and the loss of crystallinity is the most important regarding the formation of lms (Wetzel and Charalambous, 1998). While pure starch lms can be made, previous research (Zhang and Han, 2006; Lu et al., 2009) has shown them to be very brittle as a result of the strong cohesive energy density of the polymers. Plasticizers are commonly required to increase lm exibility by reduction in intramolecular hydrogen bonding along polymer chains thereby increasing the intermolecular spacing (Janjarasskul and Krochta, 2010). This results into increase in molecular mobility, lowers the glass transition temperature (Tg) and decreases the degree of the crystallinity (Guilbert et al., 1997). The plasticizers usually used are hydrophilic low molecular weight carbohydrates, such as polyols (Zhang and Han, 2006; Laohakunjit and Noomhorm, 2004; Pareta and Edirisinghe, 2005). Polyols have a tendency to adsorb water which depends on the molecular weight and number of hydroxyl groups present. Smits et al. (2003) found that the crystallisation tendency of granular potato starch can be greatly reduced when plasticizer containing more OH groups is used during gelatinisation. Adhikari et al. (2010) studied the drying behaviour of low-amylose maize starch lms plasticized by glycerol (3 hydroxyl groups) and xylitol (5 hydroxyl groups), separately and in 1:1 combination. They found xylitol to be a more effective plasticizer due to its relatively larger molecular size and tendency to form stronger hydrogen bond with starch molecules, compared to glycerol. It was concluded that xylitol plasticized lms had higher moisture migration uxes and effective moisture diffusivity values. At lower plasticizer (15% (w/w) or lower) content the combined plasticizers exhibited anti-plasticizing behaviour due to the strong hygroscopicity and hydrophilic nature of glycerol. When more than one plasticizer (other than water) was present in the system, strong plasticizer-plasticizer interactions were observed (Adhikari et al., 2010). These interactions can be cooperative which can enhance a particular properties or competitive which can retard such properties. Knowing this, a variety of plasticizers, especially polyols, at different concentrations needed to be studied to determine their effectiveness in preparing packaging lms from low amylose and high amylose starches. While a significant amount of work has been done on biodegradable packaging in the past, there has been minimal research on the presence of multiple plasticizers in starch. Furthermore, there is no comparative studies on high amylose (>70% amylose) and low amylose (25% or less) lms developed in identical conditions. In this context, this study had three main aims. Firstly, it aimed to study the gelatinisation and lm forming behaviour of low amylose and high amylose starch in the presence of plasticizers containing different hydroxyl groups (3-OH and 5-OH). Secondly, it aimed to comprehensively study the effect of the use these two plasticizers on the mechanical (tensile strength, modulus of elasticity and elongation at break) and water vapour barrier properties of plasticized high-amylose and low-amylose starch lms.

and the moisture content of the raw materials was compensated for while preparing the solution for gelatinisation. 2.2. Methods 2.2.1. Slurry preparation Slurries of starch and starchplasticizers in water were prepared using 5% (w/w) total solids on a dry weight basis using deionised water. Where starch with various plasticizers (glycerol, xylitol and glycerol + xylitol) were used, the same total solid concentration (5%, w/w) was maintained. The experimental matrix and the nomenclature of the sample are given in Table 1. In the case of low-amylose starch, starch:plasticizer ratios of 85:15, 80:20 and 70:30 were used on dry solid basis. In the case of high-amylose starch, the starchplasticizer ratios of 80:20, 70:30 and 60:40 were used on dry solid basis. Where both glycerol and xylitol are used they were used in equal amount or in (50:50) basis. 2.2.2. Gelatinisation Gelatinisation of the starch and starchplasticizer slurries was carried out using a high temperature-high pressure laboratory reactor (Amar Equipment Company, Mumbai, India). The low-amylose starch slurries were gelatinised at 100 C and at 150 rpm agitator speed. The dispersion was held for 60 min at 100 C before cooling down to 90 C. The high amylose starch was gelatinised at 130 C using 500 rpm agitator speed. The solution was held for 120 min at 130 C before cooling down to 90 C. These two time settings (60 min for low amylose starch and 120 min for high amylose starch) were chosen to allow complete gelatinisation as monitored using a polarized light microscope (Ernest Leite Wetzlar, Germany, tted with Q-Imaging camera). These gelatinised solutions were vacuumed for 20 s to eliminate entrapped air bubbles before casting commenced. 2.2.3. Film casting and conditioning Films were prepared by syringing 20 mL (in the case of LA starch) and 10 mL (in the case of HA starch) fully gelatinised dispersions, into plastic polystyrene dishes with a 90 mm diameter. Films were dried overnight at 25 1 C, in a specially designed isothermal drying box with gentle fan forced air circulation. Films were stored in a desiccator containing magnesium nitrate (52.9% RH at 25 1 C) for at least 48 h for conditioning before analysis. Triplicate experiments were carried out regarding the lm preparation. 2.2.4. Moisture content determination The moisture contents of both the starch-alone and the starch plasticizer lms were determined by a gravimetric method, whereby samples were dried at 105 0.5 C in a laboratory oven (UNE PA, Memmert, West Germany) until constant weight was achieved (Multon and Martin, 1988). Approximately 1.0 g lm samples were placed in previously dried and cooled glass petri dish and kept in the oven for 8 h. Weights of the samples were taken before and after drying using a digital balance (0.1 mg), (AE200S, Mettler, Switzerland). Tests were conducted in triplicates and the average values are reported. 2.2.5. Mechanical properties The mechanical properties such as tensile strength (MPa), modulus of elasticity (MPa) and elongation at break (%) of the starch and starchplasticizer lms were evaluated. The mechanical properties of the lms were determined in tension mode using a texture analyser (TA-XT Plus, Stable Micro Systems, UK) in accordance with ASTM method D 882 (ASTM, 2000). Tensile grips were used to hold the lms during these tensile tests. In order to promote the failure of the lms towards the centre of the lm, they

2. Materials and methods 2.1. Materials Low-amylose (LA) cornstarch with amylose:amylopectin ratio of (25:75) with 13.18% moisture and high amylose (HA) cornstarch with amylose:amylopectin ratio of (80:20) and moisture content of 12.60% were purchased through Tim Stock, Ballarat. Glycerol and xylitol were used as plasticizers and purchased from Consolidated Chemical Company, Melbourne, Victoria. Xylitol was a crystalline material and had no noticeable moisture content. The glycerol contained 2% moisture in it. All the materials were used as received

D. Muscat et al. / Journal of Food Engineering 109 (2012) 189201 Table 1 A summary of description of lm composition with code abbreviation for each lm. Abbreviation of lm LA HA LA G LA X LA GX Description of lm composition Low-amylose (26:74 amylose:amylopectin) starch without plasticizer High-amylose (80:20 amylose:amylopectin) starch without plasticizer Low-amylose starch with different percentage of glycerol, i.e. 15%, 20% and 30%, denoted as LA G15, LA G20, LA G30 Low-amylose starch with different percentage of xylitol, i.e. 15%, 20% and 30%, denoted as LA X15, LA X20, LA X30 Low-amylose starch with different percentage of glycerol and xytilol (50:50), i.e. 15%, 20% and 30%, denoted as LA GX15, LA GX20, LA GX30 High-amylose starch with different percentage of glycerol, i.e. 20%, 30% and 40%, denoted as HA G20, HA G30, HA G40 High-amylose starch with different percentage of xylitol, i.e. 20%, 30% and 40%, denoted as HA X20, HA X30, HA X40 High-amylose starch with different percentage of glycerol and xytilol (50:50), i.e. 20%, 30% and 40%, denoted as HA GX20, HA GX30, HA GX40

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mean values are reported in ensuing sections. The WVP [g mm/ (m2 h kPa)] is calculated following ASTM E96-05 protocol using Eq. (3), as follows:

WVTR

Gx A

WVP

WVTR WVTR SR1 R2 DP

HA G HA X HA GX

Where, WVTR is the water vapour transmission rate [g mm/(m2 h)]. G is the slope of the straight line representing change of vapour pressure over time (g/hr). A and x are the lm cross-section area through which the vapour gets transmitted (m2) and x is the average lm thickness (mm). Similarly, S is the saturation vapour pressure at the test temperature (kPa). R1 and R2 are relative humidity maintained by the magnesium nitrate (0.529) and calcium chloride (0.000), respectively. 2.2.7. Rheological measurements Rheological characterisation of the gelatinised starch and starchplasticizer dispersions was performed using a dynamic rheometer (RheoStress 1, Haake, GmbH, Karlsruhe, Germany). The gelatinised starch and starch-plasticized suspensions were kept at constant temperatures of 25 and 60 C for low-amylose and highamylose starch, respectively. The temperature of the high-amylose starch suspensions had to be maintained at 60 C. This is because the dispersions having high amylose starch started forming gels below this temperature. At 25 C it became impossible to maintain it as dispersion as was used to prepare lms. Silicone oil (H4160 and H4000) was used to seal the outer perimeter of the sample to prevent evaporation of the water from the edges. The temperature was kept constant (1 C) at the desired temperatures throughout test using a circulating water bath (Cool Tech 320, Thermo-Haake, Germany). Small-amplitude oscillatory tests (SAOS) were performed using a parallel plate (PP35 Ti, 35 mm diameter) and a gap of 1.00 mm between the plates. The stress and the strain responses were kept within the linear range (Gunasekaran and Mehmet, 2000). The frequency sweep tests were carried out in a frequency range of 0.0110 Hz within the linear viscoelastic region at a constant stress (20 Pa). The strain sweep tests for the low-amylose and high-amylose starch dispersions were performed at a xed frequency of 1.592 Hz and 0.045 Hz within the linear viscoelasticity region, respectively. The viscosity of the gelatinised suspensions was measured over a shear rate range of 0.0001100 s1. Storage modulus (G0 ) and loss modulus (G00 ) as a function of frequency (f) were measured for all samples. Results reported in ensuing sections are average values of at least two measurements. From the shear stress and stress rate determined from the gelatinised starch and starchplasticizer suspensions strain sweep analysis, a relationship between the two can be established. The data were tted using the HerschelBulkley relationship as given by the following equation (Steffe, 1996; Bourne, 2002):

were cut in dumbbell shape. The thickness of the lms was measured at 10 random positions in the middle part of the dumbbell shape where the failure usually occurred. A manual micrometer (Kincrome, 0.01 0.004 mm) was used for this purpose. The average value of the 10 readings was used as the lm thickness and the averaged values were subsequently sued to calculate the mechanical and water vapour barrier properties. The tensile strength (TS in Pascals) was calculated by dividing the peak force with the cross section area of the lm. Similarly the % elongation was measured by dividing the change in length achieved at break with the lms original length (0.037 m). The modulus of elasticity (EM, in Pascals) which represents the stiffness of the lms was calculated from the initial linear portion of the stressstrain curve and given by the following equation:

EM

stress F =A strain DL=L

where, F is force (N), A is the area of cross-section (m2), L and DL are the original length and the change in length in m, respectively. 2.2.6. Water vapour permeability (WVP) The water vapour permeability of the starch and starchplasticizer lms was determined using a modied ASTM E96-05 method (ASTM, 2005), as suggested by Remunan-Lopez and Bodmeier (1996). The bottles used were 22.5 mm in diameter, 42.25 mm in height and had the mouth opening of 11.50 mm. The aluminium lids used had aperture opening of 8.00 mm. Each bottle was lled with approximately 7 g of calcium chloride granules. The calcium chloride granules which passed 2.36 mm sieve were used after removing the nes (that passed through 600 lm sieve). This desiccant was pre-dried at 200 C overnight before use. The lm disc was then placed between two rubber liners, with hole of 8.00 mm in the centre and positioned to the metal lid. The liners helped maintaining a good seal between the bottle and the lid and also helped maintaining the lm integrity whilst the lm was put in place and the lid was subsequently shut. The whole unit was weighed and placed in the desiccator containing magnesium nitrate (52.9% RH). The desiccator was kept in a temperature controlled environment (Lebec Incubator, Laboratory Equipment P/L) at 20 0.5 C. Each bottle was then periodically weighed to determine extent of the water vapour transmitted through the lm as 52.9% RH gradient was maintained across the lm. In calculating WVP, linear regressions were performed graphically using weight gain versus time data. Triplicate tests were conducted and the

r r0 K cn

where, r, r0, c, K and n are shear stress (Pa), yield shear stress (Pa), consistency coefcient (Pa sn) and ow behaviour index (dimensionless), respectively. From the best t values of these parameters the nature of the uid i.e. HerschelBulkey, Bingham plastic, shearthinning and shear-thickening, etc. was determined. 2.2.8. Attenuated total reectance-fourier transform infrared analysis (ATR-FTIR) The conditioned starch-alone and starch-plasticized lms were analysed on a PerkinElmer Spectrum 000 FTIR instrument. The

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D. Muscat et al. / Journal of Food Engineering 109 (2012) 189201 Table 2 Moisture content (% wet basis) and glass transition temperature of starch alone and starchplasticizer lms equilibrated at 52.9% RH. Starch lm HA HA G20 HA G30 HA G40 HA X20 HA X30 HA X40 HA GX20 HA GX30 HA GX40 LA LA G15 LA G20 LA G30 LA X15 LA X20 LA X30 LA GX15 LA GX20 LA GX30 Moisture content (%) 14.16 0.16 12.33 0.09 24.08 0.26 25.91 0.15 8.37 0.44 9.02 0.33 10.09 0.15 9.38 0.44 17.14 0.46 24.75 0.51 12.9 0.18 10.58 0.34 13.48 0.17 25.12 0.89 10.49 0.52 10.33 0.37 9.52 0.25 9.83 0.07 10.46 0.35 16.36 0.42 Tg values (C) 67.9 2.4 51.2 1.1 34.2 0.9 Below ambient 56.1 1.9 34.2 1.7 Below ambient 55.2 1.7 Below ambient Below ambient 64.9 2.3 50.3 1.1 48.7 1.2 30.5 0.9 49.2 1.8 48.6 1.9 32.7 1.4 50.5 1.5 47.1 1.1 Below ambient

spectra were obtained in the range between 400 and 4000 cm1 wave number. 2.2.9. Differential scanning calorimetry (DSC) The glass transition temperature of the lms was determined by DSC thermograms. The samples were analysed using Metter DSC-028 (Mettler Toledo, USA). The system was calibrated for temperature and heat ux with indium (melting point 156.6 C, heat of fusion of 3.28 kJ mol1). The samples (615 mg) were weighed in aluminium pans and hermetically sealed and an empty pan was used as the reference. Scans were carried out over the temperature range of 0160 C at heating rate of 10 C min1 under nitrogen. The Tg was determined at onset of the endothermic shift in heat ow. 3. Results and discussion 3.1. Film cast formation The lms obtained were structurally intact, visually transparent, uniform and smooth. The LA and HA starch-alone lms were very brittle and cracked upon handling. These lms required extra care to retain the integrity of the lms to minimise cracking or uncontrolled fracture prior to testing. The LA G15 and LA G20 lms cracked very severely upon drying. To obtain an intact lm for the required analysis these suspensions were dried in a polystyrene dish lined with a layer of aluminium sheet as suggested by Garcia et al. (1998). The lms obtained from this altered casting method were intact upon drying. The cracking was typical of glycerol plasticized lms due to strong hydrogen bonding between glycerol and starch molecules at low concentrations of 15% and 20%, and it is referred to as anti-plasticization (Seow et al., 1999). When anti-plasticization occurs it leads to increased rigidity rather than exibility of the plasticized lm, and therefore becoming stiffer than the starch-alone LA starch lm (Chang et al., 2006). One reason for this increased rigidity is the glycerol molecules occupying sites initially occupied by water molecules and reducing the free volume available for polymer segmental mobility (Mali et al., 2008). The starchplasticizer lms having very high proportion of glycerol (e.g. HA G40) were hard to handle as they were highly sticky (adhesive) indicating those lms were in soft rubbery state at ambient temperature. In a study by Talja et al. (2007) it was reported that the lms with sticky surfaces were obtained at high plasticizer content of glycerol. All the lms were clear after drying, however, while conditioning the LA X30, HA X30 and HA X40 lms a white residue developed on the surface, referred to as blooming or blushing. This occurs when the plasticizer concentration exceeds its compatibility limit causing phase separation and physical exclusion of the plasticizer (Talja et al., 2007; Bozdemir and Tutas, 2003). Blooming was not observed in the lms having combination of plasticizers. This provides further reason why two or more plasticizers are better in forming starch-based lms. 3.2. Water content The total water content of the prepared lms are shown in Table 2. Table 2 shows that the HA starch-alone lms had slightly higher water content than the LA starch-alone lms. This may be due to the fact that amylose forms a network of stiff strands and pores present in the network could possibly entrap more water and that the water content of lms depends on the microstructure of starch network. In both the LA and HA starches the addition of glycerol signicantly increased the water content compared to the addition of xylitol due to the fact that glycerol is much more hygroscopic compared to xylitol (Smits et al., 2003). It was observed that as

the concentration of glycerol increased, the moisture content increased. The moisture contents of lms LA G20 and LA G30 were 13.48% and 25.12%, respectively, which are much higher than the moisture contents of LA X20 and LA X30 lms which were 10.33% and 9.52%, respectively. The lms plasticized with xylitol at various concentrations surprisingly had water contents of approximately 10% (w/w). The water content of all the xylitol plasticized lms were lower than that of the starch-alone LA and HA lms. The interesting aspect of this observation is the low moisture content of xylitol plasticized lms which were conditioned at 52.9% RH for 48 h. The capability of xylitol plasticized lms to equilibrate at lower moisture content even at 52.9% RH suggests that xylitol plasticized or xylitol containing lms will have reduced the hygroscopicity in the lms. The moisture content of the combined plasticizers in LA and HA lms increased as the concentration of plasticizer increased, but were lower than the lms plasticized with glycerol and higher than the lms plasticized by xylitol. 3.3. Mechanical properties The mechanical properties of the starch-alone and the polyols plasticized lms that included the tensile strength (TS), modulus of elasticity (EM) and Elongation at break (E) are summarised in Table 3. From the elongation at break values shown in this table, it can be seen that the starch-alone lms from both LA and HA fractured easily and instantly. Films with plasticizers exhibited better pliability/exibility and hence underwent fracture in a slower and more sustained pace. Films plasticized with glycerol exhibited greater pliability/exibility and hence their fracture was much slower than the lms plasticized with xylitol. Thus, with the increasing concentration of plasticizers, the fracture mechanism changed from rapid unstable brittle fracture at low strains, to elastoplastic fracture at higher strains and nally to a slow plastic fracture (Chang et al., 2006). 3.3.1. Mechanical properties of LA and HA lms As expected the starch-alone lms from both the LA and HA starches were quite strong (44.38 and 34.32 MPa). The unplasticized LA and HA lms also showed high elastic modulus of 1654 and 1685 MPa, respectively. The high TS exhibited by these unplasticized lms is attributed to the extensive intra-molecular hydrogen bonds between amylose, amylopectin and amylose amylopetin molecules in the absence of a plasticizer. A study by

D. Muscat et al. / Journal of Food Engineering 109 (2012) 189201 Table 3 Summary of tensile properties. Starch lm HA HA G20 HA G30 HA G40 HA X20 HA X30 HA X40 HA GX20 HA GX30 HA GX40 LA LA G15 LA G20 LA G30 LA X15 LA X20 LA X30 LA GX15 LA GX20 LA GX30 TS (MPa) 34.32 9.75 30.65 2.49 12.16 1.37 5.05 0.55 37.10 3.17 18.25 0.17 13.96 1.72 37.29 2.27 16.06 0.63 7.24 0.49 44.38 4.98 46.08 3.62 27.59 2.96 5.06 0.7 44.96 3.81 32.15 3.72 18.02 1.17 31.95 4.56 35.95 2.04 5.96 1.16 EM (MPa) 1685.57 88.40 1079.67 92.64 323.06 35.11 80.19 24.68 1177.57 84.59 546.57 57.40 383.69 112.44 1127.79 134.25 453.87 18.30 123.39 13.80 1654.52 245.51 1340.85 40.8 805.01 77.11 63.79 8.55 1343.65 167.82 886.72 86.15 532.9 73.17 1167.82 92.63 1009.86 44.3 108.96 13.69 E (%) 1.41 0.50 4.60 0.11 21.81 4.18 23.05 2.65 4.03 0.30 11.10 3.93 15.12 7.11 4.10 0.95 19.45 5.49 26.38 1.50 2.40 0.33 3.42 0.08 13.17 1.53 70.73 4.95 2.76 0.32 3.65 0.20 24.54 5.07 2.79 0.32 5.64 1.66 67.36 11.75 Thickness (mm) 0.065 0.001 0.056 0.005 0.065 0.004 0.051 0.011 0.053 0.002 0.057 0.003 0.055 0.003 0.059 0.001 0.057 0.002 0.059 0.001 0.120 0.004 0.135 0.004 0.140 0.003 0.132 0.011 0.116 0.009 0.149 0.020 0.123 0.005 0.150 0.021 0.139 0.012 0.147 0.009

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Moisture content (%) 14.16 0.16 12.33 0.09 24.08 0.26 25.91 0.15 8.37 0.44 9.02 0.33 10.09 0.15 9.38 0.44 17.14 0.46 24.75 0.51 12.9 0.18 10.58 0.34 13.48 0.17 25.12 0.89 10.49 0.52 10.33 0.37 9.52 0.25 9.83 0.07 10.46 0.35 16.36 0.42

Rindlav-Westling et al. (1998) observed that lms casted from high-amylose corn starch have mechanical properties in the same range as amylose lms. In general, both the LA and HA lms showed a decrease in TS at higher plasticizer contents (i.e. glycerol and xylitol). These plasticizers reduced the intra-molecular attraction between the starch chains by favourably forming hydrogen bonds between plasticizer and starch molecules. Thus reduces the formation of hydrogen bonds between the starch chains and allows greater exibility and subsequently decreases the tensile strength (Turhan and Sahbaz, 2004). As can be seen from Table 3, the decrease in tensile strength is greater with the addition of glycerol than xylitol. 3.3.2. Effect of plasticizers on tensile strength Table 3 shows that the tensile strength of glycerol-plasticized lms is always lower than the xylitol-plasticized lms at higher than 20% plasticizer concentrations. The reduction in the tensile strength with the increase in xylitol and glycerol concentrations is consistent with previous researches (Laohakunjit and Noomhorm, 2004; Chang et al., 2006; Gaudin et al., 1999). The effects of glycerol and xylitol on tensile strength in LA lms appear to be more complicated at low concentrations. The presence of both the plasticizers individually at low concentration of 15% exhibited a higher tensile strength value of 46.08 MPa for LA G15 and 44.96 MPa for LA X15 than 44.38 MPa of the LA starch lm. This phenomenon can be explained through the anti-plasticization behaviour in starchplasticizer lms when plasticizer concentration is relatively low. At low concentrations plasticizer molecules are strongly attached to the starch, restricting the starchstarch interactions necessary to absorb the mechanical energy (Marcilla and Beltran, 2004). It appears that glycerol and xylitol can exert an anti-plasticizing effect on the tensile strength of the lms when present at low concentration, i.e. 15%, in this case. This range is referred to as glycerol anti-plasticizing range by Chang et al. (2006). The lms of the LA and HA with the combined plasticizers (glycerol + xylitol) showed tensile strength values between the lms plasticized by individual plasticizers. For example, HA GX40 had a tensile strength of 7.24 MPa, which is between the tensile strength of HA G40 (5.05 MPa) and HA X40 (13.96 MPa). 3.3.3. Effect of plasticizers on modulus of elasticity Modulus of elasticity, as an index for stiffness for both types of plasticized lms, showed a general decrease with increasing

moisture content (Table 3), a behaviour expected for a plasticized material (Chang et al., 2000). The effect of the plasticizers on the modulus of elasticity of HA and LA lms could not be compared since the lm thickness were not the same for those lms (Table 3). The LA lms had thickness ranging from 0.116 to 0.150 mm which were thicker than the HA lms the thickness of which ranged from 0.051 to 0.065 mm. As shown in Table 3, the modulus of elasticity of plasticized HA lms were higher than plasticized LA lms. The modulus of elasticity decreased rapidly with the increase in the plasticizer concentration, i.e. from 1685.57 MPa for HA lm to 80.19 MPa for HA G40 lm. This rapid decrease is further compounded by the combination of plasticizers (glycerol + xylitol). The overall reduction in the modulus of elasticity for xylitol plasticized lms was greater than for glycerol plasticized lms, however, the xylitol plasticized lms had higher stiffness, and appeared rmer than the glycerol plasticized lms.

3.3.4. Effect of plasticizers on elongation at break The unplasticized LA and HA lms show the lowest values for elongation at break (2.40% and 1.41%, respectively) compared to the plasticized lms. This indicates that the (residual) water starch and starchstarch interactions in LA and HA lms produce greater number of or stronger hydrogen bonds (Turhan and Sahbaz, 2004). It can be seen in both LA and HA lms that increase in each plasticizer concentration result in an increase in the elongation. The elongation property of the lms plasticized with combined plasticizers gets signicantly improved compared to the lms plasticized only with xylitol and gets compromised compared to the lms plasticized by only glycerol. For example, LA G20 has an elongation of 13.17% while LA X20 had an elongation of 3.65%, whereas the elongation for LA GX20 was 5.64% (Table 3). From the above results it can be seen that the tensile strength, modulus of elasticity and elongation properties are strongly inuenced by the concentration of glycerol and xylitol, i.e. the concentration of plasticizers used. Mali et al. (2006) had reported the tensile strength and modulus of elasticity decreased and the elongation at break increased with increase of glycerol in various starch lms. The tabled results agree with this observation. Except in the cases where anti-plasticization occurs, the increase in the concentration of these plasticizers decreases the tensile strength and modulus of elasticity while increasing the elongation for both the LA and HA based lms. The addition of these plasticizers makes LA and HA based lms more ductile, which indicates that they oc-

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cupy the space between the starch molecules and interfere with attractive intramolecular forces. Overall, the starch lms derived from high amylose starch showed higher tensile strength and modulus of elasticity and lower elongation properties than the lms derived from low amylose starch. This can be explained through the higher gelatinisation and glass transition temperatures of the amylose fraction of starch (Lourdin et al., 1997). 3.4. Water vapour permeability (WVP) The WVP values of the starch alone and some of the polyol-plasticized lms are presented in Table 4. The WVP values of LA G15, LA X15 and LA GX15 lms are not presented as the lms showed greater extent of cracking during WVP measurements. The cracking in these lms was due to greater rigidity of starchplasticizer matrix caused by anti-plasticization. The WVP values of the LA and HA lms were 0.59 and 0.52 g mm/(m2 h kPa) respectively, as shown in Table 4. The permeability of LA lms are consistent with Talja et al. (2007), difference in our results and the authors results is due to different starch used. The potato starch used by Talja et al. (2007) would have much lower amylose content. 3.4.1. Effect of glycerol on WVP As shown in Table 4, the lms which contained glycerol as plasticizer (especially in at 30% and higher) had higher permeability values compared to the LA and HA starch-alone lms. This is because the glycerol plasticized lms tended to equilibrate at high moisture content as shown Table 3, which is consistent with earlier ndings by Gaudin et al. (2000). This study reported that higher water content leads to increased permeability in hydrophilic biopolymer lms. As shown in Table 4, both LA and HA, with 20% glycerol concentrations had a hydration capacity lower than the unplasticized lms. Then at a glycerol content of 40%, the WVP value increased. This trend was observed by Mali et al. (2004), stating this behaviour could be related to structural modications of the starch network that occurred when glycerol was added. According to Chaudhary et al. (2009), this behaviour is attributed to the molecular structure and size of the plasticizer and its interaction with water in starch matrix. Glycerol is similar to water in size and can replace water at low concentrations of glycerol to create glycerolstarch interactions forming a more compact structure, resulting in lower WVP values. To reduce these strong starch water and starchstarch interactions excess plasticizers are added (Chaudhary, 2010 ) to enhance the interactions within plasticizerplasticizer rather than with other components. Then by increasing the glycerol concentration to 40% increased the WVP values the

lm matrix became less dense, and this, added to the character of glycerol, was avourable to adsorption of water molecules, to exhibited plasticization ability. This looser network is formed due to occurrence of starchstarch interaction enhancing the mobility and exibility of the starch chains and increasing water retention in the starch matrix (Chang et al., 2006; Shaw et al., 2002). 3.4.2. Effects of xylitol on WVP From the Table 4 it can be seen that the lms with the lowest WVP values were the xylitol plasticized lms (i.e. LA X20, LA X30, HA X20, HA X30 and HA X40). Although the xylitol concentration range (2040%) was quite broad, the WVP values were almost constant at approximately 0.09 g mm/(m2 hkPa). These lms also exhibited low moisture content (Table 3) of less than 10%. With low water content present a starchwater interaction formed by hydrogen bonds is more compact than the starchstarch system (Lourdin et al., 1997). It was observed that the lms plasticized with xylitol at high concentration, i.e. LA X30, HA X30 and HA X40, exhibited blooming when they were conditioned at 52.9% RH. 3.4.3. Effect of combine plasticizers on WVP The lms plasticized with the combined plasticizers exhibited WVP values similar to the glycerol plasticized lms. At 20% combined plasticized lms the WVP values were lower than the LA and HA stand-alone lms. When the combined plasticizers concentration increased to 40% the WVP values increased. Although xylitol was also present, the glycerol concentration had a greater inuence on the interaction created, as explained earlier. Although the WVP values and moisture content of the combined plasticizers lms seem to exhibit the same trend, they were lower than the lms plasticizers by glycerol due to the presence of xylitol. These lms at high concentrations did not show signs of blooming after conditioning at 52.9% RH. Overall, 20% combined plasticized lms with both LA and HA exhibited the lowest WVP values and moisture content. 3.5. Rheological behaviour of the dispersions 3.5.1. Viscoelastic behaviour of the dispersions Frequency sweep plots of storage modulus (G0 ) and loss modulus (G00 ) of the starches and plasticized (i.e. glycerol and xylitol) suspensios at different concentrations are shown for LA (Fig. 1) and HA (Fig. 2). Both the LA and HA suspensions show lower storage modulus than the loss modulus and hence are considered to be dilute dispersions (Ikeda and Foegeding, 2005). These dispersions are formed by heating starch granules in the presence of excess water, swelling occurs causing the disruption of molecular order within the granules. With continued heating, the hydrogen bonds keeping the granule together are weakened, and irreversible swelling occurs. The granules eventually burst and solution clarity increases. This allows for the leaching of soluble components, primarily amylose into the water (BeMiller and Whistler, 1996). The viscosity of the solution rises through a maximum and then drops as the granules rupture and disintegrate (Orthoefer, 1987) resulting in dilute dispersions. These dispersions showed behaviour of entangled solution at a cross-over point at frequency of 0.2 Hz and G0 and G00 of 13.2 MPa for LA starch suspension. The HA starch suspensions had a frequency of 0.4 Hz and G0 and G00 of 0.2 MPa as the G0 became greater than G00 for the rst time at these frequencies. When the concentration of plasticizers increased the cross-over point shifted to the higher frequencies. The cross-over point for the plasticized LA suspensions increased between 1.5 to 2.2 Hz with G0 and G00 in a range of 4.1 and 12.6 MPa. The LA G15 suspension exhibited a G0 and G00 value of 14.4 MPa which was higher than the LA suspension due to anti-plasticization. The cross-over point for the plasticized HA suspension decreased

Table 4 Summary of water vapour permeability and thickness. Starch lm HA HA G20 HA G30 HA G40 HA X20 HA X30 HA X40 HA GX20 HA GX30 HA GX40 LA LA G20 LA G30 LA X20 LA X30 LA GX20 LA GX30 WVTR (g mm/m2 h) 0.55 0.03 0.46 0.12 0.56 0.04 1.34 0.07 0.12 0.02 0.09 0.01 0.07 0.02 0.15 0.02 0.26 0.04 0.71 0.04 0.63 0.14 0.28 0.01 0.68 0.05 0.11 0.03 0.11 0.01 0.13 0.02 0.21 0.02 WVP (g mm/m2 h kPa) 0.52 0.03 0.43 0.11 0.52 0.04 1.26 0.07 0.11 0.02 0.07 0.04 0.06 0.02 0.14 0.02 0.26 0.03 0.66 0.04 0.59 0.13 0.27 0.01 0.64 0.05 0.10 0.06 0.10 0.06 0.12 0.07 0.20 0.02 Thickness (mm) 0.065 0.001 0.056 0.005 0.065 0.004 0.051 0.011 0.053 0.002 0.057 0.003 0.055 0.003 0.059 0.001 0.057 0.002 0.059 0.001 0.120 0.004 0.140 0.003 0.132 0.011 0.149 0.020 0.123 0.005 0.139 0.012 0.147 0.009

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Fig. 1. Storage modulus (G) and Loss modulus (G00 ) of LA suspensions at different concentrations of plasticizers as a function of frequency (Hz). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

Fig. 2. Storage modulus (G0 ) and Loss modulus (G00 ) of HA suspensions at different concentrations of plasticizers as a function of frequency (Hz). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

slightly down to a frequency of 0.23 Hz and a G0 and G00 of 0.08 MPa. Below the frequency of cross-over point the dispersions are uid like (Ikeda and Foegeding, 2005). This cross-over point is an excellent indicator of magnitudes of average molecular weight and molecular weight distribution of the suspensions (Edwards, 2008). The G0 and G00 values of HA starch suspension were lower than those of the LA starch suspensions by a factor of 100. A study conducted by Singh et al. (2003) reported that amylose content signicantly affects the rheological properties of the starch. 3.5.2. Structure development over time of the dispersions Time sweep plots of G0 and G00 of the starch alone and starch plasticizer dispersions showed LA starch suspension is time

dependent as the G0 values increased over time. This shows that LA starch suspension is constantly undergoing molecular rearrangements favourably to an elastic solid-like nature over time (Gunasekaran and Mehmet, 2000). All the plasticized LA suspensions were time independent and the elastic nature did not change within experimental time frame used. The increase in the concentration of the plasticizers in LA suspensions decreased the elastic modulus and the viscous modulus of these suspensions. The time sweep plots shows that HA suspensions were time independent and increase of plasticizer concentration had no inuence on the elastic nature of the suspensions. The viscous (uid like) nature of the all the HA suspensions increased as the plasticizers concentration increased.

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3.5.3. Flow behaviour of the dispersions The ow curves of starch-alone and plasticized LA and HA suspensions showed that both the LA and HA suspensions were nonNewtonian in nature. The ow curves showed that the rheological behaviour can be adequately described by the HerschelBulkley model (Steffe, 1996). The shear-rate versus shear stress data of both the LA and HA suspensions followed the H-B model with correlation coefcients (R2) greater than 0.98. Most suspensions exhibited shear-thinning behaviour (n < 1) which agrees with previous reports in the literature (Bertuzzi et al., 2007; Genovese and Rao, 2003) (Table 5). As shown in Table 5, the ow behaviour index (n) values for the LA suspensions ranged between 0.55 and 0.76, n values of the HA suspensions ranged from 0.70 to 1. All these suspensions showed that a nite yield shear stress (r0) was required for all these dispersions to initiate the ow. The yield stress values of LA suspensions were higher than that of HA suspensions. From the ow behaviour index and yield stress value it can be concluded that the LA suspensions exhibit HerschelBulkley type non-Newtonian behaviour (Table 5). It was also found that the ow behaviour index decreased when the concentration of both plasticizers increased which indicates to the tendency of moving away from Newtonian behaviour. The suspensions with the combined plasticizers (glycerol + xylitol) were thinner than the plasticizers added individually to the suspension. The HA suspensions behaved as either HerschelBulkley or Bingham plastic materials. The ow behaviour indices of some of the HA suspension with higher plasticizer concentration were n = 1 (Table 5) which indicated a Newtonian behaviour. The suspensions exhibiting Bingham plastic behaviour are HA GX20, LA GX30, LA G30, LA G40, LA X40 and LA GX40.

3.6. Starchplasticizer interaction In this study, FTIR has been used to monitor microstructural characterisation of composite lm by evaluation of interactions between the lm components. The dominant functional group of carbohydrates are the hydroxyl groups which are involved in intraand inter-molecule hydrogen bonding with other hydroxyl groups (Ottenhof et al., 2003). According to Wancho and Sharma (2003), hydrogen bonding or other secondary interactions between chemical groups of dissimilar polymers should theoretically cause a shift in the peak position of participating groups. This kind of behaviour is exhibited by miscible blends that show extensive phase mixing. Depending whether the hydrogen bonding interaction shifts the wave number lower or higher will indicate if the composite lm components are forming hydrogen bonding or competing for hydrogen bonding, respectively. The shift in peak position will depend on the strength of the interaction.

3.6.1. FTIR assignment of corn starch The FTIR spectra of LA and HA lms are shown in Fig. 3. These spectra represent a typical alcohol and hydroxy compound group frequencies (Coates, 2000) and are similar to each other. FTIR assignment of corn starch includes the following frequencies. The broad band between 3000 and 3600 cm1 is attributed by the complex vibrational stretches associated with the free, inter- and intramolecular bound hydroxyl groups between neighbouring molecules, which made up the major structure of starch (Coates, 2000; Zhang and Han, 2006). Although the spectra appear to be the similar there are differences at this peak. The LA and HA lms exhibited wave numbers of 3323 and 3307 cm1, respectively. This suggests that HA lm form stronger hydrogen bonds with water due to higher proportion of amylose. The sharp peak at 2924 cm1 is characteristic of CH stretching (CH2) (Park et al., 2000). The peak occurring at 1641 cm1 is associated with the tightly bound water present in the starch (Zhang and Han, 2006) due to the hygroscopic nature of starch. The peaks at 1409 and 1433 cm1 are related to the CH bending of CH2. Peaks at 1240, 1299, and 1333 cm1 are associated to OH bending due to the primary or secondary alcohols (Coates, 2000). Changes in structure and crystallinity are reected in the focus area between 1200 and 950 cm1 which is the ngerprinting region unique for a molecule (Cerna et al., 2003; De Giacomo et al., 2008; Yao et al., 2011). Peaks 994 and 1077 cm1 are characteristic of the anhydroglucose ring OC stretching (Zhang and Han, 2006; Kacurakova and Mathlouthi, 1996). This wave number range suggests that there is a double substitution on the central hydroxyl substituted carbon and is also associated to COH bending, originated by C(4)O in the case of 1022 cm1 and C(1)H at 1047 cm1 (De Giacomo et al., 2008). The peak at 1000 cm1 is recognised as water sensitive and is related to intramolecular hydrogen bonding of hydroxyl groups (van Soest et al., 1995) or plasticizing effect of water (Kacurakova and Mathlouthi, 1996). According to Coates (2000) there is other absorption of lower importance, but often characteristic of another form of bending vibration of the OH at 720590 cm1. 3.6.2. Effect of plasticizers with LA When the LA lm was compared to LA G20 and LA G30 lms (Fig. 4) the OH stretching peak at 3324 cm1 shifted to higher wave numbers, 3344 and 3346 cm1, respectively. This shift was caused by a decrease in the intermolecular force of the hydroxyl groups between the glycerolstarch, starchwater and waterglycerol interactions. The introduction of glycerol may prevent the reformation of hydrogen bonding during the drying process as the glycerol remained and solvated between the starch polymeric chains (Zhang and Han, 2006). This suggests that the starch and glycerol were competing for hydrogen bonds with water as the glycerol concentrations increased causing the wave number to shift to a higher frequency. This nding was also observed by Park et al., (2000) were LA corn starch was plasticized with glycerol. When 15% of glycerol was added to LA starch the OH stretching peak decreased from 3324 to 3317 cm1. This indicates stronger and more stable hydrogen bonds were formed between the glycerol and starch compared with intra- and intermolecular hydrogen bonds in starch with water (Yang et al., 2006). This interaction reduces the free volume available for polymer mobility (Mali et al., 2008) causing rigidity rather than exibility of the lm, referred to as anti-plasticization (Seow, et al., 1999). The FTIR spectra for the LA-alone lm and the xylitol plasticized lms are shown in Fig. 5, where the addition of xylitol had decreased the intermolecular hydrogen bonding. This is evident at peak 3324 cm1 for LA lm had shifted to higher wavenumber, 3333 and 3324 cm1 with the addition of 20% and 30% of xylitol, respectively. The LA X30 spectrum exhibited characteristics of xylitol than LA (Fig. 5) caused by phase separation and physical exclu-

Table 5 The rheological behaviour values for the suspensions. LA suspensions Film LA LA LA LA LA LA LA LA LA LA X15 X30 G20 X20 G15 GX20 GX15 G30 GX30 K 2.13 1.80 0.92 1.54 1.98 1.90 1.64 2.27 1.63 1.57 n 0.76 0.68 0.67 0.65 0.63 0.63 0.63 0.60 0.55 0.55 HA suspensions

ro
40 20 7 15 10 20 10 12 5 7

Film HA HA HA HA HA HA HA HA HA HA X20 G20 X30 GX20 GX30 G30 X40 GX40 G40

K 0.037 0.022 0.041 0.041 0.010 0.007 0.006 0.005 0.005 0.004

n 0.86 0.82 0.75 0.70 1 1 1 1 1 1

ro
0.055 0.005 0.055 0.035 0.055 0.060 0.035 0.030 0.030 0.010

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Fig. 3. FTIR spectra of LA and HA starch lms.

Fig. 4. FTIR spectra of LA, LA G15, LA G20 and LA G30 lms.

Fig. 5. FTIR spectra of LA, LA X15, LA X20 and LA X30 lms.

sion of xylitol from the lm. It seems that 30% of xylitol had exceeds the compatibility limit of these polymers causing xylitol to separate.

The spectra of the combined plasticized LA lms were compared to the LA lm (Fig. 6) at the OH stretching region. The addition of combined plasticizers to LA affected the formation of

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Fig. 6. FTIR spectra of LA, LA GX15, LA GX20 and LA GX30 lms.

hydrogen bonds within matrix differently. At 15% there was no signicant change to the hydrogen bonds formed, i.e. no wave number shifting. At 20% the wave number increased from 3324 to 3341 cm1, suggesting a decrease in intermolecular force of the hydroxyl groups in the lm. When the concentration of combined plasticizers increased to 30% there was evidence of xylitol phase separation as the spectrum resembled the xylitol spectrum. 3.6.3. Effect of plasticizers with HA The FTIR spectra for HA lm and glycerol plasticized lms are shown in Fig. 7. The addition of 20%, 30% and 40% of glycerol to HA starch had shifted the OH stretching vibration maxima at peak 3307 cm1 to lower wavenumbers, i.e. 3238, 3242 and 3268 cm1, respectively than the HA lm. These shifts towards lower wavenumbers reveals that there is a favourable interaction between the glycerol and HA starch through the hydroxyl groups. This indicates that the preparation of composites lms with glycerol and HA starch made new hydrogen bonds between the hydroxyl groups in the glycerol molecules and the hydroxyl groups in the HA starch molecules. This new and strong hydrogen bond formation between HA starch and glycerol replaced original interaction in HA starch. The shift to lower wave numbers was observed at all the major frequencies of these spectra suggesting a strong formation of hydrogen bonds within glycerol plasticizer HA lms. The glycerol concentration of 20% exhibited a more favourable interaction between the components than at higher concentrations

of 30% and 40% due to the greater shift to a lower wavenumber (Coates, 2000). The FTIR spectra for HA lm and xylitol plasticized lms are shown in Fig. 8. The addition of 20% and 30% of glycerol to HA starch had shifted the OH stretching vibration maxima at peak 3307 cm1 to higher wavenumbers, 3317 and 3315 cm1 in comparison with the HA lm. This shift seems to indicate that the addition of xylitol led to the weakening of hydrogen bonding in the lm. Addition of xylitol may prevent the reformation of hydrogen bonding during the drying process as the xylitol remain and solvate between the starch polymeric chains (Park et al., 2000). The HA X40 spectrum exhibited characteristics of xylitol than HA (Fig. 8) caused by phase separation and physical exclusion of xylitol from the lm. It seems that 40% of xylitol had exceeds the compatibility limit of these polymers causing xylitol to separate. The spectra of the HA starch lms plasticized by combined plasticizers are shown in Fig. 9. The addition of 20%, 30% and 40% of glycerol + xylitol to HA starch had shifted the OH stretching vibration maxima at peak 3307 cm1 to higher wavenumbers, i.e. 3335, 3335 and 3343 cm1, respectively than the HA lm. This lms exhibit molecules structures and interactions similar to the 20% and 30% xylitol plasticized lms (Fig. 8). From the above discussions, it can be concluded that the addition of plasticizers to LA starch decreased the intermolecular hydrogen bonds within the lm. This was different at low concentrations of glycerol (15%) where new hydrogen bonds were formed

Fig. 7. FTIR spectra of HA, HA G20, HA G30 and HA G40 lms.

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Fig. 8. FTIR spectra of HA, HA X20, HA X30 and HA X40 lms.

Fig. 9. FTIR spectra of HA, HA GX20, HA GX30 and HA GX40 lms.

Glass transition temperature (C) .

between the LA starch and glycerol due to anti-plasticization. Additions of high concentrations of xylitol, i.e. 30% to LA starch caused phase separation of xylitol. HA lms plasticized with glycerol formed new hydrogen bonds indicating a strong interaction between the glycerol and HA starch exists with HA G20 lm exhibiting the strongest hydrogen bond interaction within the matrix. 3.7. The glass transition behaviour 3.7.1. Low-amylose starch The variation of Tg of both the LA and HA starch-alone lms are presented in Fig. 10. This gure also contains variation of Tg LA starch with glycerol and xylitol as plasticizers. The Tg values of both the HA and LA lms are very close to those reported by Lui et al., (2010) when extrapolated to the moisture content reported by these authors. Fig. 10 shows that the effect of plasticizers in lowering the Tg of the starchplasticizer lms is very strong at low moisture contents. At higher moisture contents, especially above 20% (w/w) the starchplasticizer and plasticizerwater interactions compete with the starchwater interaction. The much lowered slopes of Tg versus moisture fraction of the glycerol and xylitol plasticized starch compared to those of the starchwater lines indicate that the availability of water to rapidly lower the glass transition temperature is limited. Similarly, at higher moisture contents, the increase in the plasticizer content is unable to depress the glass transition temperature of the lms very strongly.

110 100
LA

90 80 70 60 50 40 30 20 0 0.05 0.1 0.15 0.2 0.25 0.3

HA LAG15 LAG20 LAX15 LAX20

0.35

0.4

Moisture content (fraction of total)

Fig. 10. Variation of glass transition temperature of starchwater, starchglycerol, starchxylitol lms at different moisture content.

This means that at higher moisture contents and higher plasticizer contents the three way interactions of starchwater, starchplasti-

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cizer and plasticizer-water are competitive, not synergistic when the depression in Tg of the lms is concerned. The Tg values for the LA starch lms plasticized by glycerol and/ or xylitol at different concentration are presented in Table 2. These lms were equilibrated for at least one week at 52.9% relative humidity using saturated magnesium nitrate proportion. One of the interesting features of this table is these lms equilibrate at different moisture content depending on the type and concentration of the plasticizers. As a trend, the lms with glycerol have higher equilibrium moisture content than the lms plasticized with xylitol. Interestingly, the lms plasticized with xylitol alone have equilibrium moisture contents lower than the starch-alone lms. The lms plasticized with glycerol have much higher moisture content. This shows that the glycerol has greater afnity with water. For this given relative humidity (52.9%) as the equilibrium relative moisture contents of different lms are different, the resultant Tg values of these lms are affected by the presence of this water, the type and concentration of the plasticizer in the lms. As a trend, the presence of plasticizer has lowered the Tg of the plasticized lms which is expected. For example the Tg of LA starch (at 12.9% moisture) is 64.9 C (Table 2). The Tg decreased to 30.5 and 32.7 C when 30% (on dry solid basis) of glycerol and xylitol were used as plasticizers. It has to be pointed out here that the moisture content of the LA G30 lm was 25.12% (w/w) while the xylitol plasticized lm was only 9.52% (w/w). The difference in Tg between these lms is only about 2 C. It is expected that the Tg to be depressed at least below the ambient temperature. This suggests that the xylitol has greater propensity to depress the Tg of the starch lms. The glycerol probably interacts more with water and leaves less water to plasticize the starch. The lowering of Tg of starch by plasticizer is attributed to the reduced packing of the starch molecules, which reduces the degree of crystallinity in the lm (Chang et al., 2006; Mali et al., 2008).

4. Conclusions The gelatinisation behaviour of LA and HA starch showed that HA starch needed about 30 C higher temperature and greater agitation for complete gelatinisation. Both starch-alone and plasticized starch lms (with 15% plasticizer) were brittle and cracked upon drying. Furthermore, very high xylitol concentration of 30% and above showed phase separation when conditioned at 52.9% relative humidity. The starch lms plasticized by combined plasticizers (glycerol + xylitol) did not exhibit anti-plasticization and blooming further providing reason for combining plasticizers. The starchglycerol lms had consistently higher moisture content compared to starchxylitol lms. The lms plasticized by xylitol and combination of glycerol and xylitol exhibited lower moisture contents than glycerol plasticized lms mainly due to preferred starchxylitol hydrogen bonding which allowed easy evaporation of the moisture. The tensile strength of LA lms containing low (15% dry solid basis) plasticizers was consistently higher than the tensile strength of the starch-alone lms due to anti-plasticization. When the concentration of plasticizers increased the tensile strength and the modulus of elasticity decreased, whereas the elongation at break of both the high and low amylose based lms was increased. Overall, lms with high amylose content showed higher tensile strength and modulus of elasticity values and lower elongation values than low amylose starch lms. The starch lms prepared by using 20% combined plasticizer provided the best water vapour barrier properties, and reasonable elongation, tensile strength, modulus of elasticity without any evidence of anti-plasticization. The suspensions prepared from both LA and HA starches behaved like dilute macromolecular solutions. From the ow behaviour index, the LA starch suspensions displayed Herschel Bulkley type non-Newtonian behaviour, whereas the HA starch suspensions behaved either as HerschelBulkley or Bingham plastic material. Some of the high amylose lms showed signs of crystallinity due to high moisture content or due to extra hydroxyl group present in its structure, as in the case of xylitol indicating that xylitol is able to crystallize in presence of sufcient moisture content, but when the plasticizers were combined, the phase separation associated with the xylitol was minimised, and this was attributed to the inter-plasticizer interaction within the hydrophilic starchplasticizer system.

3.7.2. High-amylose starch From Table 2 it can be seen that, the HA-alone and plasticized HA lms have generally higher Tg values than the LA-alone and plasticized LA lms. This may be due to the fact that the amylopectin fraction of starch has a lower Tg than amylose fraction (Lourdin et al., 1997). This table indicates that for the same starch:plasticizer ratio the high amylose starch based lms equilibrate at higher moisture contents than the low amylose starch based lms. Furthermore, from Fig. 10 it can be seen that the slope of Tg versus moisture content line is steeper than the similar slope in the case of low amylose starch. This indicates that there is greater possibility that the presence of both the plasticizer and water can depress the Tg of high amylose starch below room temperature faster than the low amylose starch based lms. We could not measure the Tg of HA X40, HA G 40, HA GX30, HA GX40 lm as we had only looked into the Tg above ambient temperature. As was seen in the case of LA and plasticized LA lms, the HA and plasticized HA lms equilibrated to different moisture contents and lowered the Tg differently when stored at the same relative humidity. At given moisture content, the xylitol plasticized lms had slightly higher Tg, most probably due to xylitols higher Tg (23.2 C) than that of glycerol (90 C) Furthermore, the xylitol establishes strong hydrogen bonds with the starch molecules (Chaudhary et al., 2011). The preference of starch to form hydrogen bonds with xylitol in the expense of water probably is the main reason for starchxylitol lms to have higher Tg. Overall, the xylitol plasticized HA starch lms had much lower equilibrium moisture content than the glycerol plasticized lms, which is strong indication of starchxylitol interaction in the expense of water. When water is unable to bond with starch or xylitol, it becomes easy for it to evaporate out during drying.

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