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Journal of Food Engineering 61 (2004) 459–466

Journal of Food Engineering 61 (2004) 459–466 www.elsevier.com/locate/jfoodeng Water vapor permeability, tensile

www.elsevier.com/locate/jfoodeng

Water vapor permeability, tensile properties and solubility of methylcellulose-based edible films

K. Nazan Turhan a, * , Ferhunde S ahbaz b

a Department of Food Engineering, University of Mersin, 33332 C iftlikkooy, Mersin, Turkey b 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

Water vapor permeability (WVP), tensile strength (TS), % elongation (E), adsorption capacity and % soluble matter (SM) were investigated in methylcellulose (MC) films plasticized by polyethylene glycol (PEG). The WVP of films was determined to be 0.232 · 10 10 –1.160 · 10 10 g/m s Pa, TS between 17 and 44 N/mm 2 and %E between 14% and 97%, depending on composition. Film formation was affected 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 effects. Solubility studies indicated that MC films were water-soluble and PEG containing samples had higher solu- bilities. Results suggest that mainly hydrogen bonding between PEG and MC or blocking effect in the case of high MW PEGs determine the film properties. 2003 Elsevier Ltd. All rights reserved.

Keywords: Methylcellulose films; Polyethylene glycol; Water vapor permeability; Tensile properties; Film solubility

1. Introduction

Shelf life of foods is governed by their numerous in- teractions with their surroundings and can be extended by using protective films. The deterioration of packaged foodstuffs largely depends on the transfers that may occur between the internal environment of the packaged food and the external environment. Edible films can be used to reduce water vapor, oxygen, lipid, and flavor migration between components of multicomponent food products, and between food and the surroundings. Many proteins and polysaccharides have good film- forming properties and can be used in the preparation of edible films (Greener & Fennema, 1994; Martin-Polo, 1995; McHugh & Krochta, 1994; Nisperos-Carriedo, 1994; P eerez-Gago, Nadaud, & Krochta, 1999; Torres, 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/+90-324-361- 0001; 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 films are very effi- cient barriers to oxygen and aroma compounds. Water- soluble 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 films, and is used in pharmaceutical and food industries (Donhowe

& Fennema, 1993a). MC has been combined with lipids (Greener & Fen-

nema, 1989a, 1989b; Kamper & Fennema, 1984; Kester

& Fennema, 1989; Koelsch & Labuza, 1992; Rico Pena

& Torres, 1990) and polysaccharides (Kester & Fen-

nema, 1989; Park & Chinnan, 1995) to make edible films that can serve as effective barriers to water vapor, oxy- gen and carbon dioxide. Polyethylene glycols (PEGs) with various molecular weights (MWs) are effective plasticizers for MC films (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 films. The effects of physical and morphological properties and MW of PEG, tem- perature, ethanol concentration, and film 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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K. Nazan Turhan, F. S ahbaz / Journal of Food Engineering 61 (2004) 459–466

Donhowe & Fennema, 1993a, 1993b; Kamper & Fennema, 1984; Koelsch & Labuza, 1992). The effects of relative humidity, temperature, film thickness, MW,

2.4.

Adsorption isotherms

Adsorption isotherms were determined according

and

concentration of PEG on tensile properties were

to the method proposed by Gal (1975). Equilibrium

reported (Debeaufort & Voilley, 1997; Donhowe & Fennema, 1993a, 1993b; Gennadios, Park, & Weller,

moisture content was calculated from weight gain. The dry weight of samples was determined by the oven

1993; Park et al., 1993). Moisture sorption behaviour of

method at 80 C. Equilibrium moisture content (X ) was

MC

films was investigated by Ayrancı (1996), Chinnan

expressed as grams per dry solid.

and

Park (1995), and Rico Pena and Torres (1990).

Light transmittance properties were studied by Turhan

and S ahbaz (2001).

The objectives of this work were to study some as-

pects of MC-based films including WVP, tensile pro- perties, adsorption isotherms, and solubility, as well as to evaluate the effects of film-forming solution compo- sition and plasticizers on these properties.

2. Materials and methods

2.1. Materials

MC (degree of substitution: 1.9, viscosity ¼ 500–600

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 films was prepared as described elsewhere

(Turhan, S ahbaz, & Guuner,2001) and allowed to dry at

room temperature for 24 h. Preliminary experiments were conducted using films 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 films were measured with a digital micrometer (Mitutoyo Manufacturing Co. Ltd., Japan,

sensitivity ¼ 0.001 mm) at 5 random positions on the film, following WVP and preceding tensile tests. WVP

and mechanical properties were calculated based on

average thickness.

2.5. Water vapor permeability

WVP of films was determined gravimetrically at 25 ± 1 C using a modified ASTM E96-80 (ASTM, 1983) procedure. The test film was sealed to a glass dish con- taining anhydrous calcium chloride (Merck, Darmstadt, Germany), 0% RH, and the dish was placed in a desic- cator maintained at 52 ± 2% RH with saturated mag- nesium nitrate (Merck, Darmstadt, Germany). The water vapor transferred through the film and absorbed by the desiccant was determined by measuring the weight gain. WVP was calculated from the following equation:

WVP ¼ C

x

A DP

ð1Þ

where WVP is in g/m s Pa, x is the film thickness (m), A

is area of the exposed film (m 2 ), DP is the water vapor

pressure differential across the film (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 7–10 h period. Slopes were calculated by linear re-

gression and correlation coefficient (r 2 ) for all reported

data were 0.99 or greater. At least three replicates of each film type were tested for WVP.

2.6. Tensile properties

An Instron Universal Testing Instrument (Model 1011) was used to determine film TS and %E. Testing film 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 film 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 film were tested. Tensile strength and elonga- tion properties were determined from stress–strain curves. TS was calculated by dividing the maximum load on the film before failure by the initial cross sec- tional area. The %E was obtained directly from the re- corder.

2.7. Film solubility

Films were prepared as expressed in ‘‘Film forma- tion’’ section. Seven square pieces measuring 5 · 5 cm

K. Nazan Turhan, F. S

ahbaz / Journal of Food Engineering 61 (2004) 459–466

461

were cut from each film. Samples were weighed to the

nearest 0.0001 g. One sample was placed into a perfo-

rated sample holder then immersed in a beaker con- taining 100 ml of phosphate buffer (pH ¼ 7.4 ± 0.2)

(Tuncel, C ic ek, Hayran, & Pis kin, 1995). Experiments

were carried out at 25 ± 1 C, and the buffer 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 buffer solution was filled to 100 ml in a measured flask. The soluble content of buffer solution was determined by the oven method at 80 C. For this purpose, 25 ml of buffer solution was used. The contri- bution of KH 2 PO 4 (Merck, Darmstadt, Germany) and Na 2 HPO 4 (Merck, Darmstadt, Germany) to soluble matter was also considered, and the result was corrected accordingly. The percentage of soluble matter (SM) of the films was calculated using the formula:

% SM ¼

weight loss

initial weight 100

ð2Þ

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 vari- ance (ANOVA; Statistica 6.0, StatSoft Inc., 1984– 1985). When the ANOVA test indicated a significant (p < 0:05) difference among means, a least significant difference test was used to identify which film means differed significantly.

3. Results and discussion

Preliminary studies were carried out to determine the

MC concentration for the film formulation. For this

purpose, films having MC concentration of 1.5, 3, 4, 5

and 6 g/100 ml solvent (solvent ¼ 50% ethanol) were

prepared (Table 1). As the MC concentration increased,

the solution viscosity increased. The most viscous solu-

tion could be transferred onto the casting plates, but it

spread with a little difficulty to form the film. Resulting

films having initial MC concentration of 5 and 6 g/100

ml were thicker, not transparent, had pinholes observed

even by magnifying glass, and bubbles observed by po- larized 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 film having 3 g MC/100 ml solvent were 33 ± 3 N/mm 2 and 14 ± 1%,

respectively. As the MC concentration increased to 6 g per 100 ml solvent, TS dropped to 8 ± 1 N/mm 2 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 films having 1.5 g MC/100 ml solvent had low TS and E% which could be ascribed to the being thinnest among the other films. No significant difference was detected between WVP of films (Table 1). For this reason, 3 g/100 ml solvent of MC concentration was selected for film preparation because of having the highest TS and E% within used concentrations. Effects of film-forming solution using an ethanol concentration of 25%, 50%, 67% and 75% in the solvent were investigated. As the ethanol concentration in-

creased, it became difficult to spread films on the plate, and they became more opaque and brittle. Addition

of PEG400 to the films (ethanol: 25–75%) resulted in

translucent and hazy films, but spreading was much easier. Whether the films contained PEG400 or not, the insoluble portion of MC was detected at high ethanol concentrations, even by the naked eye. The films prepared in 25% and 50% EtOH spread easily and no significant difference was detected between their WVP. But as the TS and %E of the film formed

with 50% EtOH were 33 ± 3 N/mm 2 and 14 ± 1%, those

of the film having 25% EtOH were 21 ± 2 N/mm 2 and

11 ± 2%, respectively. Therefore 50% ethanol was chosen

as the solvent to investigate the effects of PEG, and its MW and concentration on the film properties.

3.1. Adsorption isotherms

For most materials used for packaging, water vapor flux does not vary linearly with water vapor partial pressure gradient. Hydrophilic MC films exhibit non- linear sorption curves (Ayrancı, 1996; Vel aazquez de la Cruz, Torres, & Mart ıın-Polo, 2001). Consequently,

Table 1 Effect of MC concentration on the WVP and mechanical properties of films

MC (g/100 ml solvent)

Thickness (10 2 mm)

WVP (g/s m Pa) · 10 10

TS (N/mm 2 )

E (%)

1.5

1.1 ± 0.1 d

0.598 ± 0.369 a 0.514 ± 0.073 a 0.494 ± 0.152 a 0.523 ± 0.089 a 0.525 ± 0.361 a

16 ± 1 c 33 ± 3 a 23 ± 3 b 11 ± 1 d 8±1 d

10 ± 0.4 bc 14 ± 1 a 11 ± 1 b

3

1.7 ± 0.2 c

4

1.9 ± 0.2 bc

5

2.6 ± 0.5 a

8±1

cd

6

2.4 ± 0.3 ab

6±2

d

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K. Nazan Turhan, F. S ahbaz / Journal of Food Engineering 61 (2004) 459–466

4.0 3.5 g/100 mL solvent 2.64 3.0 g/100 mL solvent 1.32 2.5 g/100 mL solvent
4.0
3.5
g/100 mL solvent
2.64
3.0
g/100 mL solvent
1.32
2.5
g/100 mL solvent
0.66
2.0
1.5
1.0
0.5
0.0
0
20
40
60
80
100
X (g water/g ds)

RH (%)

Fig. 1. Adsorption isotherms of MC films containing different amounts of PEG400 (T ¼ 25 C, solvent ¼ 50% ethanol).

permeability might be expected to depend on the relative humidity (52–0%) to which the sample was exposed during testing. Ayrancı (1996) stated that the equili- brium moisture content approached to zero as the RH decreased below 35%, and at low water activities films did not adsorb water appreciably. Taking this point also into account, the adsorption isotherms of various films were determined at 25 C over the RH range of 52–98%. The equilibrium moisture content of the films was low at RH ¼ 52%, and no significant difference was detected between them. Differences were notable as the PEG400 concentration increased (Fig. 1). In all films tested, equilibrium moisture content increased almost linearly up to an a w of 0.76–0.84, where a sharp increase was noted. It was concluded that plasticization by water did not occur over the relative humidity range of experi- mental conditions. Therefore Eq. (1) can be used to calculate WVP at relative humidity difference of 52-0%, which is in linear portion of the sorption curves.

3.2. Water vapor permeability

The WVP of MC films was determined to be 0.232 · 10 10 –1.160 · 10 10 g/m s Pa depending on the film composition. WVP of MC films was reported to be between 0.87 · 10 10 and 1.47 · 10 10 g/ m s Pa (Chinnan & Park, 1995; Donhowe & Fennema, 1993a, 1993b; Kester & Fennema, 1989; Park et al., 1993; Park &

Chinnan, 1995). Experimental results were within the

literature range. MC films are characteristically hydro- philic because of the functional hydroxyl groups they

contain. Although MC is the least hydrophilic cellulose ether, MC films 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

films is 0.0022 · 10 10 and 0.0087 · 10 10 g/m s Pa, re-

spectively (Guilbert & Biquet, 1996; Myers, Meyer, Rogers, Stannet, & Szwarc, 1961). WVP of experimental

MC films were 25–500 times greater than those of syn-

thetic films. However these films are better water vapor

barriers than hydrophilic films 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 films with or without PEG400 and the effects of ethanol concentration in the film-forming so- lution were compared (Table 2). Column two shows that WVP increased significantly as the ethanol concentra-

tion increased. Ethanol is added to film-forming solu-

tions, because it allows a reduction in drying time due to its low boiling point (78 C) and does not remain in the

film

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, affects the solubility of MC, as evi-

dent from the turbid appearance of films at high ethanol

concentrations indicating incomplete solubilization. The viscosity of these film-forming solutions was high, which made the removal of air bubbles difficult, and pinholes were formed. An increase in ethanol concentration in- creased WVP. Similar results were reported in a pre- vious work (P eerez-Gago et al., 1999). However, no significant difference in WVP was found between films prepared with 0–67% ethanol concentra- tions in the presence of PEG400 (Table 2, third column). This result suggests that the plasticizing effect of PEG400 overcame the difficulties arising from the de- creasing solubility of MC as ethanol concentration in- creased. In fact, addition of PEG400 made the spreading easier, and much smoother films were obtained.

Table 2 The effects of EtOH and PEG400 on WVP

EtOH (%)

Thickness (10 2 mm)

WVP (g/s m Pa) · 10 10

No PEG400

With PEG400

No PEG400

With PEG400

0

1.5 ± 0.3 b

1.6 ± 0.3 b 1.7 ± 0.1 b 1.8 ± 0.1 b 1.8 ± 0.2 b 2.4 ± 0.3 a

0.232 ± 0.012 f 0.424 ± 0.048 ef 0.514 ± 0.073 cde 0.678 ± 0.052 bd 1.086 ± 0.295 a

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

25

1.7 ± 0.2 b

50

1.7 ± 0.2 b

67

1.7 ± 0.3 b

75

2.3 ± 0.3 a

K. Nazan Turhan, F. S

ahbaz / Journal of Food Engineering 61 (2004) 459–466

463

Addition of plasticizers to the polymer matrix results in an increase in WVP. But two different behaviors were observed in MC films. Incorporation of PEG400 to the polymer matrix resulted in an increase in WVP at low ethanol concentrations but had no effect at high con- centrations. This later result indicated that incomplete solubilization of MC still appeared as the controlling factor on the film structure; therefore, effect of PEG400 was not observed at high ethanol concentrations. The increase in WVP with increasing PEG400 con- centration is presented in Table 3. Addition of PEGs with various MWs resulted in increased WVP, although no difference was noted between their WVPs (Table 3). These were all expected results because PEG incorpo- rated to the polymer matrix decreased the attractive forces between MC chains, increased free volume and segmental motions, hence water molecules diffused more easily and higher WVP resulted. That the formation of hydrogen bonding between MC and PEG occurred, re- ducing intermolecular attraction between MC–MC chains, was also proven by the FTIR studies (Turhan et al., 2001).

3.3. Tensile properties

TS of MC films was determined to be 17–44 N/mm 2 and %E between 14 and 97 depending on the film composition. Mechanical properties for MC films were

compared as related to presence of ethanol concentra- tion and PEG400 (Table 4). The highest TS was ob- served in the film prepared with water, and addition of ethanol and PEG400 decreased TS. Increasing PEG400 concentration reduced TS, but no significant change was noted in the case of MW increase (Table 3). The high TS values, observed in the films prepared with water or water-ethanol, were attributed to the nu- merous hydrogen bonds between MC chains. These bonds contribute to cohesiveness and low flexibility of unplasticized films (Turhan et al., 2001). When PEG is incorporated in the MC network, a competition for hydrogen bonding between MC–MC and MC–PEG occurs. As a result, direct interactions between MC chains are reduced partly due to hydrogen bond for- mation with PEG or partly by the blocking effect of high-molecular-weight PEGs. The concentration of PEG400 also significantly increased the hydrogen bond formation. This was strongly in accordance with the present observation that increasing PEG400 concentra- tion 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 flexibility and de- creasing 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 effect of PEG400 concentration and MW of PEG on WVP, TS and %E

PEG400 (g/100 ml solvent)

Thickness (10 2 mm)

WVP (g/m s Pa) · 10 10

TS (N/mm 2 )

E (%)

0

1.7 ± 0.2 a

0.514 ± 0.073 d 0.620 ± 0.244 bcd 0.747 ± 0.075 ac 0.791 ± 0.089 ab 0.875 ± 0.058 a

33 ± 3 a 30 ± 3 a 25 ± 2 b 19 ± 2 c 17 ± 2 c

14 ± 1 a 20 ± 1 b 29 ± 2 c 74 ± 4 d 97 ± 4 e

0.33

1.7 ± 0.3 a

0.66

1.8 ± 0.1 a

1.32

1.8 ± 0.3 a

2.64

1.9 ± 0.2 a

PEG (MW)

400

1.8 ± 0.1 a

0.747 ± 0.075 a 0.741 ± 0.048 a 0.732 ± 0.045 a 0.667 ± 0.042 a

25 ± 2 a 23 ± 2 a 27 ± 3 a 25 ± 2 a

29 ± 2 a 32 ± 2 a 21 ± 2 b 17 ± 1 c

1450

1.6 ± 0.1 a

4000

1.6 ± 0.3 a

8000

1.7 ± 0.1 a

Means with different superscripts (a–e) are significantly different (p < 0:05). Statistical analysis for the effect 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 films

Films

Thickness (10 2 mm)

TS (N/mm 2 )

E (%)

EtOH

(0%)

1.5 ± 0.3 a 1.6 ± 0.3 a 1.7 ± 0.1 a 1.8 ± 0.2 a

44 ± 2 a 22 ± 4 c 33 ± 3 b 25 ± 2 c

14 ± 3 a 38 ± 1 b 14 ± 1 a 29 ± 1 c

EtOH

(0%) + PEG400

EtOH

(50%)

EtOH

(50%) + PEG400

Means with different superscripts (a–c) are significantly different (p < 0:05).

* 0.66 g/100 ml solvent.

464

K. Nazan Turhan, F. S ahbaz / Journal of Food Engineering 61 (2004) 459–466

on %E appeared as the PEG concentration (Table 3). Effects of PEG400 concentration on TS and %E were different (Table 3). These differences correspond to the glass transition of the polymer, which affects %E more than TS (Debeaufort & Voilley, 1997). Depending on the stress–strain curves, they classified MC-based films

into 4 groups. Using their work and the stress–strain

curves obtained in this research, the films containing no PEG were classified as brittle and in the glassy state. When PEG was incorporated, the resulting polymers

were classified as pseudoductile. Increases in %E mainly

occur when films become rubbery, i.e., when structure changes from ductile to elastic (Debeaufort & Voilley, 1997). The %E increased significantly 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 stress–strain curves. Table 3 shows that MW of PEG did not affect WVP

and TS of the films, but %E decreased slightly as the

MW of PEG increased. This can be attributed to the heterogeneous film 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

films. Potential applications may require water insolu- bility to enhance product integrity and water resistance. However, in some cases film water solubility before consumption of the product might be benefical (P eerez- Gago et al., 1999). The solubility of MC depends on its degree of sub- stitution (DS), and MC used in this research (DS ¼ 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 (Goopferich,1996). Since the hydrolysis of etheric bonds in MC was not possible in basic solution such as the phosphate buffer (pH ¼ 7.4), MC was only hydrated and dissolved in this buffer. Films prepared only with water or water/ethanol dissolved slowly, whereas plasticized film pieces dis- solved 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 MC–MC chains (Turhan et al., 2001). This effect of hydrogen bonding also was observed in tensile proper- ties. The increase in dissolution rate by the addition of PEG400 was due to the disruption of native three- dimensional structure of MC through hydrogen bond

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

t (min)

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

100 90 PEG400 PEG1450 80 PEG4000 70 PEG8000 60 50 40 30 20 10 0
100
90
PEG400
PEG1450
80
PEG4000
70
PEG8000
60
50
40
30
20
10
0
0
20
40
60
80
100
SM (%)

t (min)

Fig. 3. Effect 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 significantly increased the solution rate. This observation was in accordance with the report that in- termolecular hydrogen bonds between MC–MC 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 film water-solubility. Fig. 3 shows that %SM decreased as the MW of PEG increased. This may have resulted from the solubility and hydrophilicity differences 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 flow of water in the polymer matrix, resulting in higher dissolution rates.

4. Conclusion

MC and ethanol concentrations in film-forming so- lutions strongly affected film structure, and unacceptable films were obtained at high concentrations. WVP and

K. Nazan Turhan, F. S ahbaz / Journal of Food Engineering 61 (2004) 459–466

465

%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 effect was most pronounced on %E. This was attributed to the glass transition of the polymer to rubbery state. The films containing PEG had higher solubility, and solubility decreased as the MW of PEG increased. Structural differences between plasti- cized and unplasticized films were explained in terms of hydrogen bonding between PEG and MC chains or a blocking effect in the case of high-MW PEGs.

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