Journal of Food Engineering 105 (2011) 254263

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Journal of Food Engineering

journal homepage: www.elsevier.com/locate/jfoodeng

Biodegradable packages development from starch based heat sealable lms

Olivia V. Lpez a,, Carlos J. Lecot a, Noem E. Zaritzky a,b, Mara A. Garca a
a CIDCA (Centro de Investigacin y Desarrollo en Criotecnologa de Alimentos), Facultad de Ciencias Exactas UNLP Centro Cientco Tecnolgico La Plata (CCT-La Plata) CONICET, 47 y 116 S/N, La Plata B1900AJJ, Buenos Aires, Argentina b Facultad de Ingeniera, UNLP, Argentina

a r t i c l e

i n f o

a b s t r a c t
Heat sealing capacity of native and acetylated corn starch based lms was evaluated to develop biodegradable packages, such as bags. Thermo-mechanical properties were analyzed since they condition their handling and applications. Acetylated starch addition reinforced 80% sealing resistance of starch lms. Unplasticized heat-sealed lms presented adhesive failures while those containing glycerol showed a rupture near the zip. Unplasticized lms exhibited a single relaxation (at around 60 C), detected by DMA and conventional DSC, which was not affected by the acetylated starch content. DMA curves of plasticized lms showed two relaxations, one close to 50 C associated to the glass transition of the plasticizer-rich phase, and other around 60 C, attributed to the starch-rich phase. This last transition was also observed using MTDSC. Glycerol addition decreased the relaxation temperature of the starch-rich phase being this effect more marked in native starch lms, about 28%. A relation between lm composition, microstructure, mechanical behavior, and dynamic mechanical thermal analysis was established. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 18 November 2010 Received in revised form 3 February 2011 Accepted 18 February 2011 Available online 22 February 2011 Keywords: Biodegradable packages Heat-sealable starch lms Thermo-mechanical analysis Film composition

1. Introduction Nowadays, investigations are focussed to the development and characterization of biodegradable lms from natural polymers since conventional synthetic plastic materials are resistant to microbial attack and biodegradation (Arvanitoyannis, 1999; Fang et al., 2005). Starch has been widely used due to its low cost and renewability (Xu et al., 2005), being corn the major commercial source in the world (Mali et al., 2004). Unfortunately, this polymer has a hydrophilic nature which makes the obtained materials sensitive to the environmental humidity. In order to overcome this limitation, in a previous work acetylated corn starch lms were obtained with good water vapor barrier properties and adequate mechanical features (Lpez et al., 2008). However, this chemically modied starch is expensive; one alternative to lower the cost and extend the applications of these materials could be blended it with native corn starch. Likewise, the literature about the package development from these materials is scarce (Cho et al., 2010). For this purpose, especially for bags obtaining, is necessary that lms were able to form a good quality zip (Chillo et al., 2008). Heat sealing capacity of exible lms is critical and determined the integrity of the package. Heat sealing quality depend on the processing conditions such as temperature, time and pressure as well as previous lm treatments.
Corresponding author. Fax: +54 221 4254853/4249287.
E-mail address: ovlopez75@yahoo.com.ar (O.V. Lpez). 0260-8774/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.jfoodeng.2011.02.029

Numerous sealing techniques are available, included bar, band, impulse, wire or knife, ultrasonic, friction, gas, contact, hot-melt, pneumatic, dielectric, magnetic, induction, radiant and solvent sealing methods (Brody and Marsh, 1997). Selection of the heat sealing type depends on mainly the polymeric lm structure, the packaging and the product. Regardless the heat sealing type used, it should assure the mechanical resistance and packaging integrity preventing microorganisms entrance and maintaining its barrier properties. Sealing strength, which is a quantitative measurement used in process validation and control, is inuenced by lm thickness. Besides, the knowledge of the failure mode of a heat sealed material is critical since it conditions packaging performance and describes how the two sealed surfaces are separated during the heat sealing resistance assays. Different failure modes (adhesive, cohesive, delaminated, rupture near to the zip, rupture far to the zip, stretching and adhesive plus stretching) were described by ASTM F88-00 standard method (2001). Package handling and applications are conditioned by mechanical properties as well as thermo-mechanical behavior of lms. As is well known, starch-based lms are relative stiff being plasticizers required to produce lms less rigid and more exible (Sothornvit and Krochta, 2005). On the other hand, the glass transition temperature (Tg) is an important parameter that determines both the mechanical and barrier properties of amorphous polymers and controls the crystallization kinetics of these materials (Oxford et al., 1989). Tg of lms are commonly measured by differential scanning calorimetry

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(DSC). Dynamic thermal mechanical analysis (DMA) can be used to determine relaxation temperatures associated to glass transitions and the macro-behavior of materials caused by changes inside the lm microstructure (Arvanitoyannis et al., 1996; Lourdin et al., 1997). Many investigations (Chen et al., 2007; Thomazine et al., 2005) reported that DMA had a great functionality in measuring the viscoelastic properties of biopolymers as well as starch-based lms. Film composition can affect the Tg values; Mali et al. (2002) stressed that Tg values of yam starch lms without plasticizer were higher than those containing glycerol. A similar trend was observed for lms formulated with other polysaccharides (Debeaufort and Voilley, 1997) and proteins of varied origin (Cherian et al., 1995; Galietta et al., 1998; Sobral et al., 2001). Depending on the physical state of the material, either glassy or rubbery, its properties may be signicantly different (Arvanitoyannis, 1999). The aim of the present work was to develop biodegradable packages, such as bags, from native and acetylated corn starch lms, evaluating their heat sealing capacity. Besides, lm mechanical properties and thermo-mechanical behavior were studied to evaluate packages handling and future applications.

2.5. Film morphology Homogeneity and appearance of the lms were examined by visual observation and scanning electron microscopy (SEM) with a JEOL JSM 6360 electron microscope (Japan). For cross-section observations lms were cryofractured by immersion of the sample in liquid nitrogen. Film pieces were mounted on bronze stubs using a double-sided tape and coated with a layer of gold (4050 nm), allowing surface and cross-section visualization. All samples were examined using an accelerating voltage of 25 kV. 2.6. Mechanical properties Mechanical proles (stressstrain curves) were obtained using a texturometer TA.XT2i-Stable Micro Systems (England) with a tension grip system A/TG. Probes of 7 0.7 cm were cut; at least ten probes were used for each lm formulation. Tensile strength (TS, MPa) was calculated dividing the maximum force by lm cross-section area. Elongation at break (E, %) was calculated as the porcentual increment of probe length. Elasticity modulus (Youngs modulus, MPa) was calculated according to the ASTM D882-00 (2001) using the following equation:

2. Materials and methods 2.1. Materials Native (N) and acetylated (A) corn starches were provided by Misky, Arcor (Tucumn, Argentina). Acetylation degree of chemically modied starch was determined in a previous work, being 2.20 0.04% (Lpez et al., 2008); which is within the range recommended for food applications (up to 2.5%), by the Food and Drug Administration (FDA). Besides, glycerol (J.T. Baker, Mxico) was used as plasticizer.

Elasticity modulus

F i JD A Ai

where Fi is the registered force at a point located in the linear region of the curve (N); A is the initial area of the probe (thickness initial length) (m2); JD is the initial distance between the jaws (m) and Ai is the probe deformation at the point i (m). 2.7. Heat sealing capacity The heat seals were produced using an impulse-wire thermosealer (HermePlas, Argentina) on pieces of lms of 8.7 cm of diameter. This equipment works at 220 V leading to a xed temperature of 154.3 8.5 C which was measured using a K-type thermocouple connected to a data logger thermometer (TES-1307, Taiwan). The optimum time that allows to obtain the best zip quality was determined. Times assayed varied between 0.83 0.05 and 2.03 0.05 s. The heat-sealing resistance, which is an indicator of zip quality, was evaluated in the texturometer previously described equipped with a tension grip system A/TG using probes of 76 25 mm. The assays were performed after the heat seal was cooled down and became stable. For each lm formulation ten probes were used. Mechanical patterns were registered and failure modes were determined according to ASTM standard method F88-00 (2001). For failures where the rupture was produced near the zip, maximum traction resistance was calculated; while for adhesive, cohesive o for delamination failures, media heat sealer resistance was determined. Both resistances were expressed in MPa. In the case of adhesive failures, the necessary energy to cause the failure was also calculated as the area under the curve and expressed in J/m. 2.8. Thermo-mechanical analysis Temperatures and intensities of the relaxation phenomena in the lms were determined by DMA; glass transition temperatures were determined by DSC and MDSC. DMA assays were conducted in a dynamic-mechanical thermal equipment Q800 (TA Instruments, New Castle, USA) with a liquid N2 cooling system, using a clamp tension. Films probes with a rectangular geometry (length: 30 mm, width: 6 mm and thickness: determined as described previously) were used. To select the viscoelasticity range for further frequency sweeps, amplitude sweep

2.2. Starch lms preparation Aqueous suspensions at 5% w/w of: N, A and a blend of them in equal proportions (50N + 50A) were gelatinized at 90 C during 20 min. Furthermore, in all cases glycerol was added as plasticizer to gelatinized suspensions, at a concentration of 30 g of glycerol per 100 g of starch (30G). To obtain starch lms, approximately 20 g of lmogenic suspensions were cast onto Petri dishes (diameter 8.7 cm). They were dried in a ventilated oven at 60 C for 2 h and then they were maintained at 20 C during a week until constant weight. Films were removed from the plates and stored at 20 C and a relative humidity (RH) of 65% in a controlled temperature and humidity room.

2.3. Film humidity content It was determined measuring weight loss of lms, upon drying in an oven at 105 C until constant weight (dry sample weight). Samples were analyzed at least in duplicate and results were expressed as (%) of moisture content of samples.

2.4. Film thickness Thickness of the lms was determined using a digital coating thickness gauge Check Line DCN-900 (New York, USA) for non-conductive materials on non-ferrous substrates. Ten measurements were randomly taken at different locations for each specimen and the mean value was reported.

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were performed from 1 to 20 lm at xed frequency (5 Hz). Multifrequency sweeps (1, 3, 5, 10 and 15 Hz) at xed amplitude from 100 to 100 C at 2 C/min were carried out. The storage (E0 ) and loss (E00 ) modulus and tan d curves as a function of temperature were recorded and analyzed using the software Universal Analysis 2000. E0 is related to the mechanical energy stored per cycle when the sample is subjected to a deformation and it is the elastic response of the material. E00 is the viscous response and it is related to the dissipated energy as heat per cycle when the sample is deformed. Loss factor is dened as tan d = E00 /E0 , being d the angle between the in-phase and out-of-phase components of the modulus in the cyclic motion. Temperatures of the relaxation processes associated to glass transition temperatures were determined through the inexion point of the storage modulus E0 curve as well as the maximum peak in both the loss modulus E00 and tan d curves (Psomiadou et al., 1996). DSC analyses were performed in a differential scanning calorimeter equipment model Q100 controlled by a TA 5000 module (TA Instruments, New Castle, Delaware, USA), with a quench-cooling accessory, under a N2 atmosphere (20 ml/min). Samples (approximately 8 mg) were weighed in aluminum pans and closed hermetically; an empty pan was used as reference. The scanning rate was 2 C/min. Heating ranges were selected according to DMA results, varied from 50 to 120 C for unplasticized lms and from 70 to 100 C for plasticized ones. In both cases an annealing of 30 min at the initial heat temperature was carried out. After the rst scan was completed, the sample was cooled and then a second scan was recorded. The glass transition temperature was dened as the midpoint of the transition inection observed in thermograms using the Universal Analysis V1.7F software (TA Instruments, New Castle, USA). Modulated temperature DSC (MTDSC) was also performed using the same DSC equipment with modulated software. Hermetic pans prepared as described previously were heated and

cooled at 10 C/min. The period was 40s and the amplitude was 0.5 C. Heat ow and heat capacity curves were obtained. By splitting the total heat ow signal into a reversing (related to heat capacity) and a non-reversing component, the noise and baseline curvature are retrieved in the non-reversing signal. Therefore the detection limit of the glass transition temperature, measured via the heat capacity (reversing signal), is increased substantially (De Meuter et al., 1999). All measurements were performed at least in triplicates and reported values are the mean of measurements. 2.9. Statistical analysis All experiments were performed at least in duplicates, with individually prepared and casted lms as replicated experimental units as described previously in each determination. Systat-software (SYSTAT, Inc., Evanston, IL, USA) version 10.0 was used for multifactor analysis of variance. Differences in the properties of the lms were determined by Fishers least signicant difference (LSD) mean discrimination test, using a signicance level of a = 0.05. 3. Results and discussion Blend formulations with and without plasticizer, were able to form homogeneous lms, which were easily removed from the plates. Film forming capacity of acetylated and native starch was studied in a previous work (Lpez et al., 2008). Film thickness was signicantly affected by the composition, the higher acetylated starch concentration the higher lm thickness (Fig. 1a). These results could be attributed to the incorporation of acetyl groups which interfere in the chains alignment due to steric hindrance. SEM micrographs showed that unplasticized

Fig. 1. Composition effect on thickness and morphology (SEM micrographs) of starch based lms. (a) Film thickness; (b) cross-section of unplasticized acetylated corn starch lm; (c) cross-section of acetylated and native starch blend lm without plasticizer; (d) cross-section of acetylated starch lm plasticized with 30% (w/w) glycerol.

O.V. Lpez et al. / Journal of Food Engineering 105 (2011) 254263 Table 1 Mechanical properties and humidity content of starch lms. Film composition Tensile strength (MPa) 53.51 0.37 31.78 2.40 56.66 0.77 38.29 1.51 60.94 0.76 41.85 2.44 Elongation at break (%) 2.51 0.34 4.15 0.30 2.29 0.20 3.95 0.42 1.89 0.15 5.44 0.26 Youngs modulus (MPa) 51.49 2.66 25.16 1.02 66.50 4.18 34.67 3.44 78.54 2.82 42.46 0.31 Humidity (%) 9.08 0.13 15.68 0.38 8.43 0.42 15.75 0.51 9.04 0.01 15.28 0.91

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Native starch (N) N-30G 50N + 50A 50N + 50A-30G Acetylated starch (A) A-30G

30G: lms plasticized with 30% (w/w) glycerol. 50N + 50A: lms based on native and acetylated corn starch blend.

acetylated lms and the blend starches exhibited a multilayer structure (Fig. 1b and c). Besides, the aforementioned effect of acetylated starch addition on lm thickness was evidenced. Glycerol addition increased, in average 20%, lm thickness regardless starch type which could be related to a modication of the lm structure (Fig. 1a and d). Cross-sections of the native and the blend starch lms with 30% w/w glycerol were similar to those of acetylated starch shown in Fig. 1d. It is well known that glycerol interferes in chain interactions (Sothornvit and Krochta, 2005) and thus the typical multilayer structure of unplasticized lms was not observed. Humidity content of unplasticized lms was not affected by their composition (Table 1). As can be expected, glycerol addition increased lm humidity due to its hydrophilic character (Table 1). Hydrophilic plasticizer provides more active sites in lm matrix by exposing its hydroxyl groups in which the water molecules could be adsorbed. Besides, no signicant differences (p > 0.05) were detected in the humidity content of plasticized lms.

Starch lm mechanical behavior was evaluated through stress versus deformation curves. Figs. 2 shows the glycerol addition effect on mechanical pattern of native, acetylated and blend starch lms. Unplasticized lms resulted rigid showing the typical mechanical pattern of a brittle material which is in agreement to the multilayer lm structure evidenced by SEM. These results are similar to those reported by Mali et al. (2002, 2005) working on cassava and yam starch lms. The potential technological uses of unplasticized lms are limited and, in this work, they were developed only with comparative purposes. Glycerol addition enhanced lm exibility decreasing rupture forces and increasing lm deformation. As was previously described glycerol interference in the polymeric chain association facilitates their slipping. Thus, plasticizer incorporation modied lm mechanical prole to a exible material since tensile strength decreased and the corresponding elongation at break increased signicantly (p < 0.05) (Fig. 2). This tendency was also described by several authors working on starch lms from different sources (Chang et al., 2000; Lourdin et al., 1997; Myllarinen et al., 2002). Acetylated starch led to more resistant matrixes compared to native starch lms. Statistical analysis of the obtained results indicated that tensile strength of the lms containing acetylated starch were signicantly (p < 0.05) higher than those of native starch lms, regardless glycerol addition (Table 1). Although acetyl groups interfere with the chain alignment, they led to the development of a more resistant matrix due to the reinforcement of hydrogen bond interaction between aligned polymeric chains. Several authors have reported that structural modication of starch matrix is a useful tool to improve lm mechanical strength and barrier properties (Fringant et al., 1996, 1998; Lpez et al., 2008; Ma et al., 2009; Wilhelm et al., 2003). Youngs modulus showed a similar trend to the tensile strength (Table 1). Glycerol addition improved mechanical behavior increasing elongation at break, although this increase was signicant (p < 0.05) only in the case of acetylated starch lms (Table 1). 3.2. Heat sealing capacity

3.1. Mechanical properties The desired mechanical properties of biodegradable lms depend on their applications and subsequent transportation and handling of packaged foods.

Starch based lms were sealed by impulse sealing technique, which is widely used to zip exible synthetic lms (Brody and

70

60

50

40

30

20

10

0 0 5 10 0 5 10 0 5 10

Fig. 2. Effect of glycerol addition (30% w/w) as plasticizer on mechanical pattern of lms based on acetylated, native corn starch and their blend.

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Marsh, 1997). In this technique, jaws are heated to fusion temperature by a short powerful electric impulse. Impulse wire sealing was selected over impulse bar sealing since it allows to cool the zip, enhancing its strength, before the jaws were opened (Brody and Marsh, 1997; Osborn and Jenkins, 1992). Heat sealing ability of the developed starch lms was evaluated and the best zip quality was achieved at 154.3 8.5 C during 1.84 0.01 s for all lm formulations. A good quality zip, which determine packaging integrity, is obtained when the molecular interaction between individual layers is enough to destroy the interface and leading to a new homogenous layer (Cho et al., 2007). Fig. 3 shows the typical curves obtained from heat sealing resistance assays as well as the failure modes associated. Unplasticized lms exhibited a rupture near the zip, while plasticized ones presented adhesive failures (Fig. 3). Acetylated starch lms exhibited the higher values of the maximum traction resistance compared to native ones, while an intermediate behavior was recorded for the blend (Fig. 4). According to Lacroix (2009) the modication of functional groups such as hydroxyl, aldehyde and carboxyl acids

are responsible for the different adhesion strengths of the lms. A similar effect in polyethylene lms was described by Possart and Deckhoff (1999); the enhancement of the seal strength was attributed to the increase in chain interaction due to the incorporation of nitrogen- and oxygen- containing functional groups. Glycerol addition did not modify this tendency since plasticized acetylated starch lms exhibited statistically (p < 0.05) higher media heat sealer resistance values than those of native ones (Fig. 4). Besides, the necessary energy to cause adhesive failure of native and starch blend lms were comparable, while acetylated ones showed the highest value. Again, this was attributed to the higher resistance of acetylated matrix due to the structure reinforcement by the acetyl groups incorporation.

3.3. Thermo-mechanical properties Dynamic mechanical analysis provides information concerning the mechanical properties of solid polymeric systems, e.g. relaxa-

Fig. 3. Typical curves of heat sealing resistance and the associated failure modes of lms based on acetylated, native corn starch and their blend; (a) lms without plasticizer and (b) lms plasticized with 30% (w/w) glycerol.

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Maximum traction resistance (MPa)

a
0.4 0.3 0.2 0.1 0 NS 50NS+50AS AS

b
Media heat sealing resistance (MPa) 0.15

0.1

Energy 0.2240.003 J/m

Energy 0.240.03 J/m

Energy 0.430.04 J/m

0.05

0 NS 50NS+50AS AS

signicantly (p < 0.05) the relaxation temperature of the starchrich phase being this effect more marked in native starch lms. These results are in agreement with the well-known effect of plasticizer on glass transition temperatures (Biliaderis et al., 1999; Sothornvit and Krochta, 2005). Table 2 summarized the relaxation temperatures of the glycerol-rich phase (T1) obtained for plasticized starch lms. Plasticized starch blend lms showed higher relaxation temperatures in comparison with native and acetylated starch ones. Glycerol effect is attributed to hydrogen bonding formation between plasticizer molecules and polymeric chains, decreasing the Tg. In the case of starch blend lms, this interaction is lower, which could explain the obtained relaxation temperatures (Table 2). The temperature at which the relaxation occurs depends on the frequency used in the assays. This effect is illustrated for the glycerol-rich phase of the native starch plasticized with 30% (w/w) glycerol (Fig. 6). The inexion point of the E curve as well as the maximum peak in both the E00 and tan d curves shifted to higher temperatures with increasing frequencies (Fig. 6). This tendency was also observed by Biliaderis et al. (1999) working on pullulan-starch blend lms. Besides, Ma et al. (2009) stressed that loss factor was sensitive to molecular motion and its peak was related to the glass transition temperature. Apparent activation energy (DHa) for the transition can be determined from the Arrhenius rate relationship

Fig. 4. Heat sealing resistance of lms based on acetylated, native corn starch and their blend (a) maximum traction resistance of unplasticized lms and (b) media heat sealing resistance of 30% (w/w) glycerol plasticized lms and the necessary energy to cause adhesive failure.

ln f

DH a RT g

tion mechanisms, compatibility of polymer blends, damping properties and curing rate of polymeric systems (Demirgz et al., 2000). The linear viscoelastic range was around 12 lm for all starch lm formulations studied. Thus, frequency sweep assays as a function of temperature was performed at constant amplitude of 5 lm. Fig. 5a shows E0 (storage modulus), E00 (loss modulus) and tan d dependence with temperature of acetylated corn starch lms plasticized with 30% glycerol. Several authors stressed that starch glycerol mixtures are partially miscible systems, given rise to starch-rich phase and other rich in glycerol (Da Roz et al., 2006; Garca et al., 2009; Mathew and Dufresne, 2002). Likewise, Zhang and Han (2006) stressed that glycerol miscibility in starch matrix is limited and depends on plasticizer concentration. Thus, plasticized lm dynamic-mechanical patterns show two relaxations, one located around 50 C (T1), associated to the glass transition of the plasticizer-rich phase, and other about 60 C (T2), attributed to the starch-rich phase (Fig. 5a). The transition at around 50 C showed a better denition with a higher associated intensity change than that about 60 C. Our results are in agreement with those reported by Jiang et al. (2006) working on thermoplastic acetylated tapioca starch lms. A similar trend was also reported by other authors for lms formulated with native starches from different sources such as barley (Forsell et al., 1997), waxy maize (Garca et al., 2009), pea (Ma et al., 2009), mungbean (Hongsprabhas and Israkarn, 2008), cassava (Fam et al., 2006) and cara (Wilhelm et al., 2003) roots. This tendency was also informed for plasticized protein lms (Cherian et al., 1995). Dynamic-mechanical patterns of unplasticized lms exhibited a single relaxation, in comparison with those containing glycerol; this trend is shown for tan d curves in Fig. 5b. Biliaderis et al. (1999) stressed that systems based on polymer-water presented only one transition. In unplasticized lms, relaxation temperatures of the starch-rich phase, were not affected by the acetylated corn starch percentage in the formulation (Fig. 5c). Psomiadou et al. (1996) working on corn starch lms informed a Tg value similar to those obtained in the present work. Glycerol addition decreased

where f is the frequency of mechanical oscillation (115 Hz), DHa is the apparent activation energy, R is the universal gas constant and Tg is the glass transition temperature. The mathematical tting of Arrhenius equation to experimental data of the relaxation temperature associated to Tg values of the glycerol-rich phase, as a function of the frequency is shown in Fig. 7. A satisfactory correlation was found (r2 > 0.94) for plasticized lms formulated with different types of corn starch. The apparent activation energy values obtained in the present work (Fig. 7) are within the range of those reported in literature (102 400.3 kJ/mol) for starch based plasticized lms depending on lm composition (Biliaderis et al., 1999; Zhang and Han, 2006). Although the obtained DHa values were closer, the highest value corresponded to acetylated starch lms (289.30 kJ/mol). This could indicate that starch polymeric chains require more energy from the environment to overcome the cohesive forces. Besides, evidences of this reinforcement of the acetylated starch matrix were described in the lm mechanical behavior. DSC experiments allowed the determination of Tg in unplasticized lms; the obtained results were 74.8 2.3 C for native starch lms; 71.7 3.2 for acetylated ones and 71.5 3.4 C for the starch blend. Tg values obtained by DSC were in agreement with the relaxation temperatures determined by DMA (Fig. 5c) for unplasticized lms; these temperatures were not signicantly affected (p > 0.05) by the type of starch used in lm formulation. In the case of plasticized lms, Tg could not be detected by conventional DSC, although two heat scans were carried out. Several authors described that this procedure helps to the Tg detection in DSC assays (Fam et al., 2006; Rivero et al., 2010). Measurement of Tg by DSC in starch samples is difcult since the change of heat capacity or the signal on heat ow is usually weaker than that of conventional polymers. Thus, for plasticized lms it was necessary to use the MTDSC technique; De De Meuter et al. (1999) reported that this technique is the most adequate for the Tg detection in thermoplastic starch materials. Plasticized lms Tg values were around 30% lower than those of unplasticized ones, indicating the well known effect of

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3

1x10 1x10
4

1x10

-1

Storage modulus

Tan Delta

Storage Modulus (MPa)

1x10 8x10
3

-1

Loss modulus
8x10
-2

6x10

6x10

6x10 4x10
3

-2

4x10

Tan Delta

4x10

-2

2x10 2x10
3

2x10 0 100

-2

0 -100 -50 0 50

Temperature (C)

b
0.14 0.12

0.10

53.36 C 50N+50A-30G

Tan Delta

0.08

0.06

0.04

0.02

65.25 C 50N+50A
0.00 -100 -50 0 50 100

Temperature (C)

c
80

Relaxation temperature of starch-rich

0G
phase through Tan Delta (C)
70

30G
60 50 40 30 20 10 0

50N+50A

Fig. 5. Dynamic mechanical analysis of starch based lms: (a) isochronal evolution of storage modulus (E0 ), loss modulus (E00 ) and loss factor (tan d) as a function of temperature of plasticized acetylated corn starch lm; (b) isochronal evolution of loss factor (tan d) as a function of temperature of acetylated and native starch blend (50N + 50A) lm unplasticized and with 30% (w/w) glycerol addition; (c) composition effect on the relaxation temperatures of the starch-rich phase (obtained through tan d curves) of starch based lms.

Loss Modulus (MPa)

1x10

1x10

-1

8x10

O.V. Lpez et al. / Journal of Food Engineering 105 (2011) 254263 Table 2 Relaxation temperatures (T1) associated to the glass transition of the glycerol-rich phase of starch lms plasticized with 30% (w/w) glycerol determined by DMA (10 Hz). Plasticized lm composition Relaxation temperatures (T1) associated to the glass transition of the glycerol-rich phase (C) Inexion of storage modulus (E0 ) Native Acetylated Starch blend 60.92 0.01 58.85 1.73 56.90 3.94 Maximum of loss modulus (E00 ) 61.06 4.11 56.28 1.75 55.67 0.14 Maximum of tan d 52.24 0.30 48.78 1.63 45.03 0.42

261

3.5 3 2.5 ln f 2 1.5 1 0.5 0 4.25 4.5 1000/Tg (1/C)

Fig. 7. Arrhenius plot of ln frequency versus reciprocal of the relaxation temperatures associated to the glass transition of the glycerol-rich phase of plasticized lms based on acetylated, native corn starch and their blend. Correlation coefcient (r2) and apparent activation energy (DHa) for the transitions are indicated for each lm composition.
Native starch r 2 = 0.9822 Ha=247.48 kJ/mol Blend starch r 2 = 0.9427 Ha=243.91 kJ/mol Acetylated starch r 2 = 0.9692 Ha=289.30 kJ/mol

4.75

glycerol on starch matrixes. Thermal transitions observed by MTDSC were weak and broad; so DMA is a more precise technique for the detection of starch-rich phase glass transition, since it involves a clearer associated signal change. 3.4. Relationship between thermo-mechanical properties and microstructural properties of the lms Mechanical properties of unplasticized lms (shown in Table 1) can be related to the relaxation temperatures obtained by DMA and Tg values determined by DSC or MDSC. At ambient temperature, unplasticized lms, with a multilayer structure, are brittle with a low humidity content and exhibited high tensile strength and low values of deformation at break (Table 1); this behavior can be attributed to the vitreous condition of the matrix (Tg > 25 C). Films plasticized with glycerol showed high humidity content (Table 1). The plasticizing action, attributed to a combined effect of both components (glycerol and water), increases polymer chains mobility due to the major free volume available decreasing the relaxation temperature of the starch-rich phase (Fig. 5c).

Accordingly, low tensile strength and high elongations were observed for plasticized lms (Table 1). Regardless glycerol addition, lm tensile strength measured by mechanical resistance assays (Table 1) increased in the following sequence: native starch < starch blend < acetylated starch. A similar trend was observed in the values of the storage modulus (E0 ) at 20 C (temperature at which mechanical assays were determined) being: 331, 430 and 832 MPa for unplasticized native starch, starch blend, and acetylated starch lms, respectively. For both plasticized and unplasticized lms, the height of the relaxation peak (tan d vs temperature curves) of the starch-rich phase (Fig. 5b) is in good agreement with the lm mechanical behavior (Table 1); the higher the height of the relaxation peak,

Fig. 6. Frequency effect on relaxation temperature of glycerol-rich phase of native starch plasticized with 30% (w/w) of glycerol and storage (E0 ), loss modulus (E00 ) and loss factor (tan d) curves.

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O.V. Lpez et al. / Journal of Food Engineering 105 (2011) 254263 Chillo, S., Flores, S., Mastromatteo, M., Conte, A., Gerschenson, Del., Nobile, M., 2008. Inuence of glycerol and chitosan on tapioca starch-based edible lm properties. Journal of Food Engineering 88, 159168. Cho, S., Ullsten, H., Gllstedt, M., Hedenqvist, M., 2007. Heat-sealing properties of compression-molded wheat gluten lms. Journal of Biobased Material and Bioenergy 1, 5663. Cho, S., Yun Lee, S., Rhee, C., 2010. Edible oxygen barrier bilayer lm pouches from corn zein and soy protein isolate for olive oil packaging. Food Science and Technology 43, 12341239. Da Roz, A., Carvalho, A., Gandini, A., Curvelo, A., 2006. The effects of plasticizers on thermoplastic starch compositions obtained by melt processing. Carbohydrate Polymer 63, 417424. De Meuter, P., Rahier, H., Van Mele, B., 1999. The use of modulated temperature differential scanning calorimetry for the characterisation of food systems. International Journal of Pharmaceutics 192, 7784. Debeaufort, F., Voilley, A., 1997. Methylcellulose-based edible lms and coatings: 2. Mechanical and thermal properties as a function of plasticizer content. Journal of Agricultural and Food Chemistry 45, 685689. Demirgz, D., Elvira, C., Mano, J., 2000. Chemical modication of starch based biodegradable polymeric blends: effects on water uptake, degradation behaviour and mechanical properties. Polymer Degradation and Stability 70, 161170. Fam, L., Flores, S., Gerschenson, L., Goyanes, S., 2006. Physical characterization of cassava starch biolms with special reference to dynamic mechanical properties at low temperatures. Carbohydrate Polymer 66, 815. Fang, J., Fawler, P., Eserig, C., Gonzlez, R., Costa, J., Chamudis, L., 2005. Development of biodegradable laminate lms derived from naturally occurring carbohydrate polymers. Carbohydrate Polymer 60, 3942. Forsell, P., Mikkil, J., Moates, G., Parker, R., 1997. Phase and glass transitions behaviour of concentrated barley starchglycerol mixtures, a model for thermoplastic starch. Carbohydrate Polymer 34, 275282. Fringant, C., Desbrires, J., Rinaudo, M., 1996. Physical properties of acetylated starch-base de materials: relation with their molecular characteristics. Polymer 37, 26632673. Fringant, C., Rinaudo, M., Foray, M., Bardet, M., 1998. Preparation of mixed esters of starch or use of an external plasticizers: two different ways to change the properties of starchsorbitol lms. Carbohydrate Polymer 35, 97106. Galietta, G., Di-Gioia, L., Guilbert, S., Cuq, B., 1998. Mechanical and thermomechanical properties of lms based on whey proteins as affected by plasticizer and crosslinking agents. Journal of Dairy Science 81, 31233130. Garca, N., Fam, L., Dufresne, A., Aranguren, M., Goyanes, S., 2009. A Comparison between the Properties of Tuber and Cereal Starches. Food Research International. doi:10.1016/j.foodres.2009-05-004. Hongsprabhas, P., Israkarn, K., 2008. New insights on the characteristics of starch network. Food Research International 41, 9981006. Jiang, W., Qiao, X., Sun, K., 2006. Mechanical and thermal properties of thermoplastic acetylated starch/poly (ethylene-co-vinyl alcohol) blends. Carbohydrate Polymer 65, 139143. Lacroix, M., 2009. Mechanical and permeability properties of edible lms and coatings for food and pharmaceutical applications. In: Embuscado, M.E., Huber, K.C. (Eds.), Edible Films and Coatings for Food Applications. Springer, New York, USA, pp. 347366. Lpez, O., Garca, M., Zaritzky, N., 2008. Film forming capacity of chemically modied corn starches. Carbohydrate Polymers 73, 573581. Lourdin, D., Bizot, H., Colonna, P., 1997. Antiplasticization in starch glycerol lms. Journal of Applied Polymer Science 63, 10471053. Ma, X., Chang, P., Yu, J., Stumborg, M., 2009. Properties of biodegradable citric acidmodied granular starch/thermoplastic pea starch composites. Carbohydrate Polymer 75, 18. Mali, S., Grossmann, M., Garca, M., Martino, M., Zaritzky, N., 2002. Microstructural characterization of yam starch lms. Carbohydrate Polymer 50, 379386. Mali, S., Karam, L., Pereira Ramos, L., Grossmann, M., 2004. Relationships among the composition and physicochemical properties of starches with the characteristics of their lms. Journal of Agricultural and Food Chemistry 52, 77207725. Mali, S., Grossmann, M., Garca, M., Martino, M., Zaritzky, N., 2005. Mechanical and thermal properties of yam starch lms. Food Hydrocolloids 19, 157164. Mathew, A., Dufresne, A., 2002. Plasticized waxy maize starch: effect of polyols and relative humidity on material properties. Biomacromolecules 3, 11011108. Myllarinen, P., Partanen, R., Seppala, J., Forsell, P., 2002. Effect of glycerol on behaviour of amylose and amylopectin lms. Carbohydrate Polymer 50, 355 361. Osborn, K., Jenkins, W., 1992. Plastic Films: Technology and Packaging Applications. Technomic Publishing Co., Inc., Pennsylvania, USA. Oxford, P., Parker, R., Ring, S., 1989. Effect of water as a diluent on the glass transition behaviour of malto-oligosaccharides, amylase and amylopectin. International Journal of Biological Macromolecules 11, 9196. Possart, W., Deckhoff, S., 1999. Adhesion mechanism in a cyanurate prepolymer on silicon and on aluminium. International Journal of Adhesion and Adhesives 19, 425434. Psomiadou, E., Arvanitoyannis, I., Yamamoto, N., 1996. Edible lms made from natural resources; microcrystalline cellulose (MCC), methylcellulose (MC) and corn starch and polyols: Part 2. Carbohydrate Polymer 31, 194204. Rivero, S., Garca, M., Pinotti, A., 2010. Correlation between structural, barrier thermal and mechanical properties of plasticized gelatin lm. Innovative Food Science and Emerging Technologies. 11, 369375.

the higher the lm ductility. A similar trend was reported by Fringant et al. (1998) working on starch acetate lms. Thus, a correlation between microstructural properties and lm mechanical behavior was found. 4. Conclusions All the developed lms showed a good heat sealing capacity of the developed lms and the optimum conditions were established. Acetylated starch addition in lm formulation reinforced the sealing resistance. Heat sealing tests showed that unplasticized lms exhibited adhesive failures while those containing glycerol presented a rupture near the zip. Glycerol addition in starch lms was required, leading to a more ductile and exible material, improving lm handling. The addition of plasticizer decreased the relaxation temperature of the starchrich phase (T2) being this effect more marked in native starch lms. Besides, apparent activation energy of the glycerol-rich phase relaxation (T1) was determined and the highest value corresponded to plasticized acetylated starch lms. For all tested lms tensile strength, storage modulus (E0 ) and height of the relaxation peak (tan d vs temperature curves) of the starch-rich phase, showed a similar trend: native starch < starch blend < acetylated starch. Thus, lm composition, was related to microstructure, mechanical behavior, dynamic mechanical analysis and Tg determined by DSC and MTDSC. The replacement of 50% acetylated corn starch by native one is an economically viable alternative to obtain resistant but ductile lms plasticized with 30% w/w glycerol, with adequate heat sealing properties allowing the development of biodegradable packages, such as bags. Further research could be focussed on the evaluation of the matrix polymeric ability as carrier of active substances. Besides, the use and performance of these biodegradable bags to specic applications such as food, agronomic and pharmaceutical products should be studied. Acknowledgements The nancial support provided by Universidad Nacional de La Plata, ANPCyT (Project PICT 758) of Argentina was gratefully acknowledged. Authors wish to thank Misky Arcor (Argentina) for providing modied starch samples. References
American Society for Testing and Materials ASTM, 2001a. Standard Test Method for Tensile Properties of Thin Plastic Sheeting ASTM D882-00, vol. 08.01. ASTM Standards on Disc. ASTM, Philadelphia, p. 9. American Society for Testing and Materials ASTM, 2001b. Standard Test Method for Seal Strength of Flexible Barrier Materials ASTM F88-00, vol. 15.09. ASTM Standards on Disc. ASTM, Philadelphia, p.6. Arvanitoyannis, I., 1999. Totally-and-partially biodegradable polymer blends based on natural and synthetic macromolecules: preparation and physical properties and potential as food packaging materials. Journal of Macromolecular Science Review in Macromolecular Chemistry and Physics C39 (2), 205271. Arvanitoyannis, I., Psomiadou, E., Nakayama, A., 1996. Edible lms made from sodium caseinate, starches, sugars or glycerol: Part 1. Carbohydrate Polymer 31, 179192. Biliaderis, C., Lazaridou, A., Arvanitoyannis, I., 1999. Glass transition and physical properties of polyol-plasticised pullulanstarch blends at low moisture. Carbohydrate Polymer 40, 2947. Brody, A., Marsh, K., 1997. Wiley Encyclopedia of Packaging Technology. John Wiley and Sons, New York. Chang, Y., Cheah, P., Seow, C., 2000. Plasticizingantiplasticizing effects of water on physical properties of tapioca starch lms in the glassy state. Journal of Food Science 65, 445451. Chen, K., Li, D., Wang, I., zkan, N., Chen, X., Mao, Z., 2007. Dynamic viscoelastic properties of rice kernels studied by dynamic mechanical analyzer. International Journal of Food Engineering 3 (2), 114. Cherian, G., Gennadios, A., Weller, C., Chinachoti, P., 1995. Thermo-mechanical behavior of wheat gluten lms: effect of sucrose, glycerin, and sorbitol. Cereal Chemistry 72, 16.

O.V. Lpez et al. / Journal of Food Engineering 105 (2011) 254263 Sobral, P., Menegalli, F., Hubinger, M., Roques, M., 2001. Mechanical, water vapour barrier and thermal properties of gelatin based edible lms. Food Hydrocolloids 15, 423432. Sothornvit, R., Krochta, J., 2005. Plasticizers in edible lms and coatings. In: Han, J.H. (Ed.), Innovations in Food Packagings. Elsevier, Amsterdam, The Netherlands, pp. 403428. Thomazine, M., Carvalho, R., Sobral, P., 2005. Physical properties of gelatin lms plasticized by blends of glycerol and sorbitol. Journal of Food Science 70, 172 176.

263

Wilhelm, H., Sierakowski, M., Souza, G., Wypych, F., 2003. Starch lms reinforced with mineral clay. Carbohydrate Polymer 52, 101110. Xu, Y., Kim, K., Hanna, M., Nag, D., 2005. Chitosanstarch composite lm: preparation and characterization. Industrial Crops and Products 21, 185192. Zhang, Y., Han, J., 2006. Mechanical and thermal characteristics of pea starch lms plasticized with monosaccharides and polyols. Journal of Food Science 71, 109 118.