Journal of Food Engineering 61 (2004) 459466 www.elsevier.

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Water vapor permeability, tensile properties and solubility of methylcellulose-based edible lms
K. Nazan Turhan
a b

a,*

, Ferhunde Sahbaz

Department of Food Engineering, University of Mersin, 33332 C iftlikky, Mersin, Turkey o Department of Food Engineering, Hacettepe University, 06532 Beytepe, Ankara, Turkey

Received 10 July 2001; received in revised form 14 August 2002; accepted 29 April 2003

Abstract Water vapor permeability (WVP), tensile strength (TS), % elongation (E), adsorption capacity and % soluble matter (SM) were investigated in methylcellulose (MC) lms plasticized by polyethylene glycol (PEG). The WVP of lms was determined to be 0.232 1010 1.160 1010 g/m s Pa, TS between 17 and 44 N/mm2 and %E between 14% and 97%, depending on composition. Film formation was aected by MC concentration, ethanol percent in the solution and the presence of PEG. Incorporation of various molecular weight (MW) PEGs to the polymer matrix increased both WVP and %E, decreased TS. Increase in PEG400 concentration had similar eects. Solubility studies indicated that MC lms were water-soluble and PEG containing samples had higher solubilities. Results suggest that mainly hydrogen bonding between PEG and MC or blocking eect in the case of high MW PEGs determine the lm properties. 2003 Elsevier Ltd. All rights reserved.
Keywords: Methylcellulose lms; Polyethylene glycol; Water vapor permeability; Tensile properties; Film solubility

1. Introduction Shelf life of foods is governed by their numerous interactions with their surroundings and can be extended by using protective lms. The deterioration of packaged foodstus largely depends on the transfers that may occur between the internal environment of the packaged food and the external environment. Edible lms can be used to reduce water vapor, oxygen, lipid, and avor migration between components of multicomponent food products, and between food and the surroundings. Many proteins and polysaccharides have good lmforming properties and can be used in the preparation of edible lms (Greener & Fennema, 1994; Martin-Polo, 1995; McHugh & Krochta, 1994; Nisperos-Carriedo, 1994; Prez-Gago, Nadaud, & Krochta, 1999; Torres, e 1994; Zagory, 1995).

* Corresponding author. Address: Department of Food Science, University of Wisconsin-Madison, 1605 Linden Drive Babcock Hall 3B, Madison, WI 53706, USA. Tel.: +1-608-262-2784/+90-324-3610001; fax: +1-608-262-6872/+90-324-361-0032. E-mail addresses: knazan@mersin.edu.tr, boyaci99@yahoo.com (K. Nazan Turhan).

Cellulose-derivative-based edible lms are very ecient barriers to oxygen and aroma compounds. Watersoluble cellulose derivatives such as methylcellulose (MC) are of interest to researchers because they are able to form a continuous matrix. MC is a cellulose ether that exhibits thermal gelation, forms excellent lms, and is used in pharmaceutical and food industries (Donhowe & Fennema, 1993a). MC has been combined with lipids (Greener & Fennema, 1989a, 1989b; Kamper & Fennema, 1984; Kester & Fennema, 1989; Koelsch & Labuza, 1992; Rico Pena & Torres, 1990) and polysaccharides (Kester & Fennema, 1989; Park & Chinnan, 1995) to make edible lms that can serve as eective barriers to water vapor, oxygen and carbon dioxide. Polyethylene glycols (PEGs) with various molecular weights (MWs) are eective plasticizers for MC lms (Debeaufort & Voilley, 1997; Donhowe & Fennema, 1993b; Park, Weller, Vergano, & Testin, 1993). Several studies were carried out to determine water vapor permeability (WVP), tensile strength (TS) and % elongation (E) of MC-based lms. The eects of physical and morphological properties and MW of PEG, temperature, ethanol concentration, and lm thickness on WVP were investigated (Chinnan & Park, 1995;

0260-8774/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0260-8774(03)00155-9

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Donhowe & Fennema, 1993a, 1993b; Kamper & Fennema, 1984; Koelsch & Labuza, 1992). The eects of relative humidity, temperature, lm thickness, MW, and concentration of PEG on tensile properties were reported (Debeaufort & Voilley, 1997; Donhowe & Fennema, 1993a, 1993b; Gennadios, Park, & Weller, 1993; Park et al., 1993). Moisture sorption behaviour of MC lms was investigated by Ayranc (1996), Chinnan and Park (1995), and Rico Pena and Torres (1990). Light transmittance properties were studied by Turhan and Sahbaz (2001). The objectives of this work were to study some aspects of MC-based lms including WVP, tensile properties, adsorption isotherms, and solubility, as well as to evaluate the eects of lm-forming solution composition and plasticizers on these properties.

2.4. Adsorption isotherms Adsorption isotherms were determined according to the method proposed by Gal (1975). Equilibrium moisture content was calculated from weight gain. The dry weight of samples was determined by the oven method at 80 C. Equilibrium moisture content (X ) was expressed as grams per dry solid. 2.5. Water vapor permeability WVP of lms was determined gravimetrically at 25 1 C using a modied ASTM E96-80 (ASTM, 1983) procedure. The test lm was sealed to a glass dish containing anhydrous calcium chloride (Merck, Darmstadt, Germany), 0% RH, and the dish was placed in a desiccator maintained at 52 2% RH with saturated magnesium nitrate (Merck, Darmstadt, Germany). The water vapor transferred through the lm and absorbed by the desiccant was determined by measuring the weight gain. WVP was calculated from the following equation: x WVP C 1 ADP where WVP is in g/m s Pa, x is the lm thickness (m), A is area of the exposed lm (m2 ), DP is the water vapor pressure dierential across the lm (Pa), and C is the slope of the weight gain of the dish, to the nearest 0.0001 g, versus time. Generally ten weighings were taken over a 710 h period. Slopes were calculated by linear regression and correlation coecient (r2 ) for all reported data were 0.99 or greater. At least three replicates of each lm type were tested for WVP. 2.6. Tensile properties An Instron Universal Testing Instrument (Model 1011) was used to determine lm TS and %E. Testing lm specimens were rectangular strips 38 mm long and 5.79 mm wide as suggested in ASTM D683M (ASTM, 1993). A strain rate of 50 mm/min was used. All lm strips were equilibrated for one week to 52 2% RH in a cabinet using saturated magnesium nitrate solution at room temperature (25 1 C). At least four replicates of each MC lm were tested. Tensile strength and elongation properties were determined from stressstrain curves. TS was calculated by dividing the maximum load on the lm before failure by the initial cross sectional area. The %E was obtained directly from the recorder. 2.7. Film solubility Films were prepared as expressed in Film formation section. Seven square pieces measuring 5 5 cm

2. Materials and methods 2.1. Materials MC (degree of substitution: 1.9, viscosity 500600 cP) was obtained from British Drug House (Poole, England), PEG400 was obtained from Hopkins and Williams, PEG1450 from Sigma (St. Louis, MO, USA), PEG4000 from British Drug House (Poole, England) and PEG8000 from Aldrich (Steinhem, Germany). 2.2. Film formation The MC lms was prepared as described elsewhere (Turhan, Sahbaz, & Gner, 2001) and allowed to dry at u room temperature for 24 h. Preliminary experiments were conducted using lms of 1.5, 3, 4, 5 or 6 g MC in 100 ml 50% ethanol solution. Film prepared from 3 g MC in 100 ml 50% ethanol was determined as the most feasible one. Then experiments were carried out adding 3 g MC in 100 ml into I 0%, 25%, 67% and 75% ethanol solution, II solutions in I plus 0.66 g PEG400, III 50% ethanol solution plus 0.66 g PEG1450, 4000, 8000, IV 50% ethanol solution plus 0.33, 1.32 or 2.64 g PEG400. 2.3. Film thickness Thicknesses of lms were measured with a digital micrometer (Mitutoyo Manufacturing Co. Ltd., Japan, sensitivity 0.001 mm) at 5 random positions on the lm, following WVP and preceding tensile tests. WVP and mechanical properties were calculated based on average thickness.

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were cut from each lm. Samples were weighed to the nearest 0.0001 g. One sample was placed into a perforated sample holder then immersed in a beaker containing 100 ml of phosphate buer (pH 7.4 0.2) (Tuncel, Cicek, Hayran, & Pis kin, 1995). Experiments were carried out at 25 1 C, and the buer solution was continuously mixed by a magnetic stirrer at 500 rpm. At the end of 10 min, the sample holder was removed, and the volume of buer solution was lled to 100 ml in a measured ask. The soluble content of buer solution was determined by the oven method at 80 C. For this purpose, 25 ml of buer solution was used. The contribution of KH2 PO4 (Merck, Darmstadt, Germany) and Na2 HPO4 (Merck, Darmstadt, Germany) to soluble matter was also considered, and the result was corrected accordingly. The percentage of soluble matter (SM) of the lms was calculated using the formula: % SM weight loss 100 initial weight 2

This experiment was carried out for 20, 30, 45, 60, 75, and 90 min. Each run was repeated three times, and the arithmetic mean was reported. 2.8. Statistical analysis Data were initially evaluated using analysis of variance (ANOVA; Statistica 6.0, StatSoft Inc., 1984 1985). When the ANOVA test indicated a signicant (p < 0:05) dierence among means, a least signicant dierence test was used to identify which lm means diered signicantly.

3. Results and discussion Preliminary studies were carried out to determine the MC concentration for the lm formulation. For this purpose, lms having MC concentration of 1.5, 3, 4, 5 and 6 g/100 ml solvent (solvent 50% ethanol) were prepared (Table 1). As the MC concentration increased, the solution viscosity increased. The most viscous solution could be transferred onto the casting plates, but it spread with a little diculty to form the lm. Resulting lms having initial MC concentration of 5 and 6 g/100
Table 1 Eect of MC concentration on the WVP and mechanical properties of lms MC (g/100 ml solvent) 1.5 3 4 5 6 Thickness (102 mm) 1.1 0.1 1.7 0.2c 1.9 0.2bc 2.6 0.5a 2.4 0.3ab
d

ml were thicker, not transparent, had pinholes observed even by magnifying glass, and bubbles observed by polarized microscope. Their turbid appearance indicated incomplete solubilization of MC at high concentrations. They had low barrier and mechanical properties (Table 1). For example, the TS and %E of the lm having 3 g MC/100 ml solvent were 33 3 N/mm2 and 14 1%, respectively. As the MC concentration increased to 6 g per 100 ml solvent, TS dropped to 8 1 N/mm2 and %E to 6 2%. The decrease in mechanical properties with increasing MC concentration may be explained by the partial MC insolubility at high concentrations. On the other hand the lms having 1.5 g MC/100 ml solvent had low TS and E% which could be ascribed to the being thinnest among the other lms. No signicant dierence was detected between WVP of lms (Table 1). For this reason, 3 g/100 ml solvent of MC concentration was selected for lm preparation because of having the highest TS and E% within used concentrations. Eects of lm-forming solution using an ethanol concentration of 25%, 50%, 67% and 75% in the solvent were investigated. As the ethanol concentration increased, it became dicult to spread lms on the plate, and they became more opaque and brittle. Addition of PEG400 to the lms (ethanol: 2575%) resulted in translucent and hazy lms, but spreading was much easier. Whether the lms contained PEG400 or not, the insoluble portion of MC was detected at high ethanol concentrations, even by the naked eye. The lms prepared in 25% and 50% EtOH spread easily and no signicant dierence was detected between their WVP. But as the TS and %E of the lm formed with 50% EtOH were 33 3 N/mm2 and 14 1%, those of the lm having 25% EtOH were 21 2 N/mm2 and 11 2%, respectively. Therefore 50% ethanol was chosen as the solvent to investigate the eects of PEG, and its MW and concentration on the lm properties. 3.1. Adsorption isotherms For most materials used for packaging, water vapor ux does not vary linearly with water vapor partial pressure gradient. Hydrophilic MC lms exhibit nonlinear sorption curves (Ayranc, 1996; Velzquez de la a Cruz, Torres, & Martn-Polo, 2001). Consequently,

WVP (g/s m Pa) 1010 0.598 0.369 0.514 0.073a 0.494 0.152a 0.523 0.089a 0.525 0.361a
a

TS (N/mm2 ) 16 1 33 3a 23 3b 11 1d 8 1d
c

E (%) 10 0.4bc 14 1a 11 1b 8 1cd 6 2d

Means with dierent superscripts (ad) are signicantly dierent (p < 0:05). * Solvent: 50% ethanol.

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X (g water/g ds)

3.0 2.5 2.0 1.5 1.0 0.5 0.0 0

2.64 g/100 mL solvent 1.32 g/100 mL solvent 0.66 g/100 mL solvent

20

40

60

80

100

RH (%)

Fig. 1. Adsorption isotherms of MC lms containing dierent amounts of PEG400 (T 25 C, solvent 50% ethanol).

permeability might be expected to depend on the relative humidity (520%) to which the sample was exposed during testing. Ayranc (1996) stated that the equilibrium moisture content approached to zero as the RH decreased below 35%, and at low water activities lms did not adsorb water appreciably. Taking this point also into account, the adsorption isotherms of various lms were determined at 25 C over the RH range of 5298%. The equilibrium moisture content of the lms was low at RH 52%, and no signicant dierence was detected between them. Dierences were notable as the PEG400 concentration increased (Fig. 1). In all lms tested, equilibrium moisture content increased almost linearly up to an aw of 0.760.84, where a sharp increase was noted. It was concluded that plasticization by water did not occur over the relative humidity range of experimental conditions. Therefore Eq. (1) can be used to calculate WVP at relative humidity dierence of 52-0%, which is in linear portion of the sorption curves. 3.2. Water vapor permeability The WVP of MC lms was determined to be 0.232 1010 1.160 1010 g/m s Pa depending on the lm composition. WVP of MC lms was reported to be between 0.87 1010 and 1.47 1010 g/ m s Pa (Chinnan & Park, 1995; Donhowe & Fennema, 1993a, 1993b; Kester & Fennema, 1989; Park et al., 1993; Park &
Table 2 The eects of EtOH and PEG400 on WVP EtOH (%) Thickness (102 mm) No PEG400 0 25 50 67 75 1.5 0.3 1.7 0.2b 1.7 0.2b 1.7 0.3b 2.3 0.3a
b

Chinnan, 1995). Experimental results were within the literature range. MC lms are characteristically hydrophilic because of the functional hydroxyl groups they contain. Although MC is the least hydrophilic cellulose ether, MC lms are still poor moisture barriers (Barrie, 1968; Biquet & Labuza, 1988; De Leiris, 1994; Kamper & Fennema, 1984; Pascat, 1985; Schwartzberg, 1985). For example, WVP of high and low density polyethylene lms is 0.0022 1010 and 0.0087 1010 g/m s Pa, respectively (Guilbert & Biquet, 1996; Myers, Meyer, Rogers, Stannet, & Szwarc, 1961). WVP of experimental MC lms were 25500 times greater than those of synthetic lms. However these lms are better water vapor barriers than hydrophilic lms based on starch, casein, and wheat gluten (Allen, Nelson, Steinberg, & McGill, 1963; Aydt, Weller, & Testin, 1991; Gontard & Guilbert, 1994; Greener & Fennema, 1989b; Kester & Fennema, 1989; Schultz, Miers, Owens, & Maclay, 1949). The WVP of lms with or without PEG400 and the eects of ethanol concentration in the lm-forming solution were compared (Table 2). Column two shows that WVP increased signicantly as the ethanol concentration increased. Ethanol is added to lm-forming solutions, because it allows a reduction in drying time due to its low boiling point (78 C) and does not remain in the lm after drying. Therefore it does not strongly modify the structure of the polymer (Debeaufort & Voilley, 1997; Turhan et al., 2001). The ethanol concentration, on the other hand, aects the solubility of MC, as evident from the turbid appearance of lms at high ethanol concentrations indicating incomplete solubilization. The viscosity of these lm-forming solutions was high, which made the removal of air bubbles dicult, and pinholes were formed. An increase in ethanol concentration increased WVP. Similar results were reported in a previous work (Prez-Gago et al., 1999). e However, no signicant dierence in WVP was found between lms prepared with 067% ethanol concentrations in the presence of PEG400 (Table 2, third column). This result suggests that the plasticizing eect of PEG400 overcame the diculties arising from the decreasing solubility of MC as ethanol concentration increased. In fact, addition of PEG400 made the spreading easier, and much smoother lms were obtained.

WVP (g/s m Pa) 1010 With PEG400 1.6 0.3 1.7 0.1b 1.8 0.1b 1.8 0.2b 2.4 0.3a
b

No PEG400 0.232 0.012 0.424 0.048ef 0.514 0.073cde 0.678 0.052bd 1.086 0.295a
f

With PEG400 0.697 0.010bc 0.745 0.042b 0.747 0.075b 0.829 0.054b 1.160 0.247a

Means with dierent superscripts (af) are signicantly dierent (p < 0:05). * PEG400 0.66 g/100 ml solvent.

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Addition of plasticizers to the polymer matrix results in an increase in WVP. But two dierent behaviors were observed in MC lms. Incorporation of PEG400 to the polymer matrix resulted in an increase in WVP at low ethanol concentrations but had no eect at high concentrations. This later result indicated that incomplete solubilization of MC still appeared as the controlling factor on the lm structure; therefore, eect of PEG400 was not observed at high ethanol concentrations. The increase in WVP with increasing PEG400 concentration is presented in Table 3. Addition of PEGs with various MWs resulted in increased WVP, although no dierence was noted between their WVPs (Table 3). These were all expected results because PEG incorporated to the polymer matrix decreased the attractive forces between MC chains, increased free volume and segmental motions, hence water molecules diused more easily and higher WVP resulted. That the formation of hydrogen bonding between MC and PEG occurred, reducing intermolecular attraction between MCMC chains, was also proven by the FTIR studies (Turhan et al., 2001). 3.3. Tensile properties TS of MC lms was determined to be 1744 N/mm2 and %E between 14 and 97 depending on the lm composition. Mechanical properties for MC lms were

compared as related to presence of ethanol concentration and PEG400 (Table 4). The highest TS was observed in the lm prepared with water, and addition of ethanol and PEG400 decreased TS. Increasing PEG400 concentration reduced TS, but no signicant change was noted in the case of MW increase (Table 3). The high TS values, observed in the lms prepared with water or water-ethanol, were attributed to the numerous hydrogen bonds between MC chains. These bonds contribute to cohesiveness and low exibility of unplasticized lms (Turhan et al., 2001). When PEG is incorporated in the MC network, a competition for hydrogen bonding between MCMC and MCPEG occurs. As a result, direct interactions between MC chains are reduced partly due to hydrogen bond formation with PEG or partly by the blocking eect of high-molecular-weight PEGs. The concentration of PEG400 also signicantly increased the hydrogen bond formation. This was strongly in accordance with the present observation that increasing PEG400 concentration decreased TS, due to increase of hydrogen bonding. Therefore PEGs reduce intermolecular attraction by forming hydrogen bonds between MC chains or by blocking the chains, allowing more exibility and decreasing TS. The incorporation of PEG to the polymer matrix increased %E (Table 4). While the increase in MW of PEG decreased %E slightly, the most profound factor

Table 3 The eect of PEG400 concentration and MW of PEG on WVP, TS and %E PEG400 (g/100 ml solvent) 0 0.33 0.66 1.32 2.64 PEG (MW) 400 1450 4000 8000 Thickness (102 mm) 1.7 0.2 1.7 0.3a 1.8 0.1a 1.8 0.3a 1.9 0.2a 1.8 0.1a 1.6 0.1a 1.6 0.3a 1.7 0.1a
a

WVP (g/m s Pa) 1010 0.514 0.073 0.620 0.244bcd 0.747 0.075ac 0.791 0.089ab 0.875 0.058a 0.747 0.075a 0.741 0.048a 0.732 0.045a 0.667 0.042a
d

TS (N/mm2 ) 33 3 30 3a 25 2b 19 2c 17 2c 25 2a 23 2a 27 3a 25 2a
a

E (%) 14 1a 20 1b 29 2c 74 4d 97 4e 29 2a 32 2a 21 2b 17 1c

Means with dierent superscripts (ae) are signicantly dierent (p < 0:05). Statistical analysis for the eect of the concentration of PEG400 and the MW of PEG were made independently. * 0.66 g/100 ml solvent.

Table 4 Tensile properties of various lms Films EtOH EtOH EtOH EtOH (0%) (0%) + PEG400 (50%) (50%) + PEG400 Thickness (102 mm) 1.5 0.3a 1.6 0.3a 1.7 0.1a 1.8 0.2a TS (N/mm2 ) 44 2a 22 4c 33 3b 25 2c E (%) 14 3a 38 1b 14 1a 29 1c

Means with dierent superscripts (ac) are signicantly dierent (p < 0:05). * 0.66 g/100 ml solvent.

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100 90 80 70 SM (%) 60 50 40 30 20 10 0 0 20 40 t (min) 60 80 100
%50 EtOH + PEG400 %0 EtOH + PEG400 %50 EtOH %0 EtOH

SM (%)

on %E appeared as the PEG concentration (Table 3). Eects of PEG400 concentration on TS and %E were dierent (Table 3). These dierences correspond to the glass transition of the polymer, which aects %E more than TS (Debeaufort & Voilley, 1997). Depending on the stressstrain curves, they classied MC-based lms into 4 groups. Using their work and the stressstrain curves obtained in this research, the lms containing no PEG were classied as brittle and in the glassy state. When PEG was incorporated, the resulting polymers were classied as pseudoductile. Increases in %E mainly occur when lms become rubbery, i.e., when structure changes from ductile to elastic (Debeaufort & Voilley, 1997). The %E increased signicantly with the PEG400 content. At high PEG400 concentrations, the polymer deforms homogeneously by viscous processes, given a large extension to failure. This also was observed from the shape of stressstrain curves. Table 3 shows that MW of PEG did not aect WVP and TS of the lms, but %E decreased slightly as the MW of PEG increased. This can be attributed to the heterogeneous lm structure arising from the decrease of solubility and miscibility of high-molecular-weight PEGs. 3.4. Film solubility Solubility in water is an important property of edible lms. Potential applications may require water insolubility to enhance product integrity and water resistance. However, in some cases lm water solubility before consumption of the product might be benecal (Preze Gago et al., 1999). The solubility of MC depends on its degree of substitution (DS), and MC used in this research (DS 1.9) was reported as water-soluble (Kirk & Othmer, 1963 1972). The dissolution of a hydrophilic polymer such as MC involves the penetration of water to the polymer bulk and swelling. This is followed by disruption of hydrogen and Van der Walls forces between polymer chains. Chemical degradation leading to the creation of oligomers and monomers occurs via hydrolysis or enzyme-catalysed hydrolysis (Gpferich, 1996). Since o the hydrolysis of etheric bonds in MC was not possible in basic solution such as the phosphate buer (pH 7.4), MC was only hydrated and dissolved in this buer. Films prepared only with water or water/ethanol dissolved slowly, whereas plasticized lm pieces dissolved rapidly after coming into contact with water (Fig. 2). The low dissolution rate indicated the high cohesion of MC matrix via numerous hydrogen bonds between MCMC chains (Turhan et al., 2001). This eect of hydrogen bonding also was observed in tensile properties. The increase in dissolution rate by the addition of PEG400 was due to the disruption of native threedimensional structure of MC through hydrogen bond

Fig. 2. Eect of solution concentration and PEG400 (0.66 g/100 ml solvent) and on solubility.

100 90 80 70 60 50 40 30 20 10 0 0 20 40 60 80 100
PEG400 PEG1450 PEG4000 PEG8000

t (min)

Fig. 3. Eect of MW of PEG (0.66 g/100 ml solvent) on solubility.

formation with PEG400. This result also was supported by experiments during which the concentration of PEG400 signicantly increased the solution rate. This observation was in accordance with the report that intermolecular hydrogen bonds between MCMC chains were replaced by hydrogen bonds with PEG400 (Turhan et al., 2001). As a result, the solvation of polar sites on the MC chains and reduced intermolecular attraction may be accountable for increased lm water-solubility. Fig. 3 shows that %SM decreased as the MW of PEG increased. This may have resulted from the solubility and hydrophilicity dierences between PEG molecules, since both properties decrease with an increase in MW. In addition, higher numbers of edge groups in low MW PEGs enable faster ow of water in the polymer matrix, resulting in higher dissolution rates.

4. Conclusion MC and ethanol concentrations in lm-forming solutions strongly aected lm structure, and unacceptable lms were obtained at high concentrations. WVP and

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%E increased and TS decreased with the addition of various MW PEGs to the polymer matrix. Increasing PEG400 concentration increased WVP and %E and decreased TS, but its eect was most pronounced on %E. This was attributed to the glass transition of the polymer to rubbery state. The lms containing PEG had higher solubility, and solubility decreased as the MW of PEG increased. Structural dierences between plasticized and unplasticized lms were explained in terms of hydrogen bonding between PEG and MC chains or a blocking eect in the case of high-MW PEGs. References
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