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Water vapor permeability, tensile properties and solubility of


methylcellulose-based edible films

Article  in  Journal of Food Engineering · February 2004


DOI: 10.1016/S0260-8774(03)00155-9

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Journal of Food Engineering 61 (2004) 459–466
www.elsevier.com/locate/jfoodeng

Water vapor permeability, tensile properties


and solubility of methylcellulose-based edible films
a,* b
K. Nazan Turhan , Ferhunde S
ß ahbaz
a
Department of Food Engineering, University of Mersin, 33332 C
ß iftlikk€oy, 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

Abstract
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 · 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 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 Cellulose-derivative-based edible films are very effi-


cient barriers to oxygen and aroma compounds. Water-
Shelf life of foods is governed by their numerous in- soluble cellulose derivatives such as methylcellulose
teractions with their surroundings and can be extended (MC) are of interest to researchers because they are able
by using protective films. The deterioration of packaged to form a continuous matrix. MC is a cellulose ether
foodstuffs largely depends on the transfers that may that exhibits thermal gelation, forms excellent films, and
occur between the internal environment of the packaged is used in pharmaceutical and food industries (Donhowe
food and the external environment. Edible films can be & Fennema, 1993a).
used to reduce water vapor, oxygen, lipid, and flavor MC has been combined with lipids (Greener & Fen-
migration between components of multicomponent food nema, 1989a, 1989b; Kamper & Fennema, 1984; Kester
products, and between food and the surroundings. & Fennema, 1989; Koelsch & Labuza, 1992; Rico Pena
Many proteins and polysaccharides have good film- & Torres, 1990) and polysaccharides (Kester & Fen-
forming properties and can be used in the preparation of nema, 1989; Park & Chinnan, 1995) to make edible films
edible films (Greener & Fennema, 1994; Martin-Polo, that can serve as effective barriers to water vapor, oxy-
1995; McHugh & Krochta, 1994; Nisperos-Carriedo, gen and carbon dioxide. Polyethylene glycols (PEGs)
1994; Perez-Gago, Nadaud, & Krochta, 1999; Torres, with various molecular weights (MWs) are effective
1994; Zagory, 1995). plasticizers for MC films (Debeaufort & Voilley, 1997;
Donhowe & Fennema, 1993b; Park, Weller, Vergano,
& Testin, 1993).
Several studies were carried out to determine water
*
Corresponding author. Address: Department of Food Science, vapor permeability (WVP), tensile strength (TS) and %
University of Wisconsin-Madison, 1605 Linden Drive Babcock Hall elongation (E) of MC-based films. The effects of physical
3B, Madison, WI 53706, USA. Tel.: +1-608-262-2784/+90-324-361-
0001; fax: +1-608-262-6872/+90-324-361-0032.
and morphological properties and MW of PEG, tem-
E-mail addresses: knazan@mersin.edu.tr, boyaci99@yahoo.com perature, ethanol concentration, and film thickness
(K. Nazan Turhan). 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
460 K. Nazan Turhan, F. Sß ahbaz / Journal of Food Engineering 61 (2004) 459–466

Donhowe & Fennema, 1993a, 1993b; Kamper & 2.4. Adsorption isotherms
Fennema, 1984; Koelsch & Labuza, 1992). The effects
of relative humidity, temperature, film thickness, MW, 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 & moisture content was calculated from weight gain. The
Fennema, 1993a, 1993b; Gennadios, Park, & Weller, 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 2.5. Water vapor permeability
and Sß ahbaz (2001).
The objectives of this work were to study some as- WVP of films was determined gravimetrically at
pects of MC-based films including WVP, tensile pro- 25 ± 1 C using a modified ASTM E96-80 (ASTM, 1983)
perties, adsorption isotherms, and solubility, as well as procedure. The test film was sealed to a glass dish con-
to evaluate the effects of film-forming solution compo- taining anhydrous calcium chloride (Merck, Darmstadt,
sition and plasticizers on these properties. 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
2. Materials and methods water vapor transferred through the film and absorbed
by the desiccant was determined by measuring the
2.1. Materials weight gain. WVP was calculated from the following
equation:
MC (degree of substitution: 1.9, viscosity ¼ 500–600 x
WVP ¼ C ð1Þ
cP) was obtained from British Drug House (Poole, ADP
England), PEG400 was obtained from Hopkins and where WVP is in g/m s Pa, x is the film thickness (m), A
Williams, PEG1450 from Sigma (St. Louis, MO, USA), is area of the exposed film (m2 ), DP is the water vapor
PEG4000 from British Drug House (Poole, England) pressure differential across the film (Pa), and C is the
and PEG8000 from Aldrich (Steinhem, Germany). slope of the weight gain of the dish, to the nearest 0.0001
g, versus time. Generally ten weighings were taken over
2.2. Film formation a 7–10 h period. Slopes were calculated by linear re-
gression and correlation coefficient (r2 ) for all reported
The MC films was prepared as described elsewhere data were 0.99 or greater. At least three replicates of
(Turhan, Sß ahbaz, & G€
uner, 2001) and allowed to dry at each film type were tested for WVP.
room temperature for 24 h. Preliminary experiments
were conducted using films of 1.5, 3, 4, 5 or 6 g MC in 2.6. Tensile properties
100 ml 50% ethanol solution. Film prepared from 3 g
MC in 100 ml 50% ethanol was determined as the most An Instron Universal Testing Instrument (Model
feasible one. Then experiments were carried out adding 1011) was used to determine film TS and %E. Testing
3 g MC in 100 ml into film specimens were rectangular strips 38 mm long and
5.79 mm wide as suggested in ASTM D683M (ASTM,
I 0%, 25%, 67% and 75% ethanol solution, 1993). A strain rate of 50 mm/min was used. All film
II solutions in I plus 0.66 g PEG400, strips were equilibrated for one week to 52 ± 2% RH in a
III 50% ethanol solution plus 0.66 g PEG1450, 4000, cabinet using saturated magnesium nitrate solution at
8000, room temperature (25 ± 1 C). At least four replicates of
IV 50% ethanol solution plus 0.33, 1.32 or 2.64 g each MC film were tested. Tensile strength and elonga-
PEG400. tion properties were determined from stress–strain
curves. TS was calculated by dividing the maximum
2.3. Film thickness load on the film before failure by the initial cross sec-
tional area. The %E was obtained directly from the re-
Thicknesses of films were measured with a digital corder.
micrometer (Mitutoyo Manufacturing Co. Ltd., Japan,
sensitivity ¼ 0.001 mm) at 5 random positions on the 2.7. Film solubility
film, following WVP and preceding tensile tests. WVP
and mechanical properties were calculated based on Films were prepared as expressed in ‘‘Film forma-
average thickness. tion’’ section. Seven square pieces measuring 5 · 5 cm
K. Nazan Turhan, F. Sß ahbaz / Journal of Food Engineering 61 (2004) 459–466 461

were cut from each film. Samples were weighed to the ml were thicker, not transparent, had pinholes observed
nearest 0.0001 g. One sample was placed into a perfo- even by magnifying glass, and bubbles observed by po-
rated sample holder then immersed in a beaker con- larized microscope. Their turbid appearance indicated
taining 100 ml of phosphate buffer (pH ¼ 7.4 ± 0.2) incomplete solubilization of MC at high concentrations.
(Tuncel, Cß icßek, Hayran, & Pisßkin, 1995). Experiments They had low barrier and mechanical properties (Table
were carried out at 25 ± 1 C, and the buffer solution was 1). For example, the TS and %E of the film having 3 g
continuously mixed by a magnetic stirrer at 500 rpm. At MC/100 ml solvent were 33 ± 3 N/mm2 and 14 ± 1%,
the end of 10 min, the sample holder was removed, and respectively. As the MC concentration increased to 6 g
the volume of buffer solution was filled to 100 ml in a per 100 ml solvent, TS dropped to 8 ± 1 N/mm2 and %E
measured flask. The soluble content of buffer solution to 6 ± 2%. The decrease in mechanical properties with
was determined by the oven method at 80 C. For this increasing MC concentration may be explained by the
purpose, 25 ml of buffer solution was used. The contri- partial MC insolubility at high concentrations. On the
bution of KH2 PO4 (Merck, Darmstadt, Germany) and other hand the films having 1.5 g MC/100 ml solvent
Na2 HPO4 (Merck, Darmstadt, Germany) to soluble had low TS and E% which could be ascribed to the being
matter was also considered, and the result was corrected thinnest among the other films. No significant difference
accordingly. The percentage of soluble matter (SM) of was detected between WVP of films (Table 1). For this
the films was calculated using the formula: reason, 3 g/100 ml solvent of MC concentration was
weight loss selected for film preparation because of having the
% SM ¼  100 ð2Þ highest TS and E% within used concentrations.
initial weight
Effects of film-forming solution using an ethanol
This experiment was carried out for 20, 30, 45, 60, 75, concentration of 25%, 50%, 67% and 75% in the solvent
and 90 min. Each run was repeated three times, and the were investigated. As the ethanol concentration in-
arithmetic mean was reported. creased, it became difficult to spread films on the plate,
and they became more opaque and brittle. Addition
2.8. Statistical analysis of PEG400 to the films (ethanol: 25–75%) resulted in
translucent and hazy films, but spreading was much
Data were initially evaluated using analysis of vari- easier. Whether the films contained PEG400 or not, the
ance (ANOVA; Statistica 6.0, StatSoft Inc., 1984– insoluble portion of MC was detected at high ethanol
1985). When the ANOVA test indicated a significant concentrations, even by the naked eye.
(p < 0:05) difference among means, a least significant The films prepared in 25% and 50% EtOH spread
difference test was used to identify which film means easily and no significant difference was detected between
differed significantly. their WVP. But as the TS and %E of the film formed
with 50% EtOH were 33 ± 3 N/mm2 and 14 ± 1%, those
of the film having 25% EtOH were 21 ± 2 N/mm2 and
3. Results and discussion 11 ± 2%, respectively. Therefore 50% ethanol was chosen
as the solvent to investigate the effects of PEG, and its
Preliminary studies were carried out to determine the MW and concentration on the film properties.
MC concentration for the film formulation. For this
purpose, films having MC concentration of 1.5, 3, 4, 5 3.1. Adsorption isotherms
and 6 g/100 ml solvent (solvent ¼ 50% ethanol) were
prepared (Table 1). As the MC concentration increased, For most materials used for packaging, water vapor
the solution viscosity increased. The most viscous solu- flux does not vary linearly with water vapor partial
tion could be transferred onto the casting plates, but it pressure gradient. Hydrophilic MC films exhibit non-
spread with a little difficulty to form the film. Resulting linear sorption curves (Ayrancı, 1996; Velazquez de la
films having initial MC concentration of 5 and 6 g/100 Cruz, Torres, & Martın-Polo, 2001). Consequently,

Table 1
Effect of MC concentration on the WVP and mechanical properties of films
MC (g/100 ml solvent) Thickness (102 mm) WVP (g/s m Pa) · 1010 TS (N/mm2 ) E (%)
d a c
1.5 1.1 ± 0.1 0.598 ± 0.369 16 ± 1 10 ± 0.4bc
3 1.7 ± 0.2c 0.514 ± 0.073a 33 ± 3a 14 ± 1a
4 1.9 ± 0.2bc 0.494 ± 0.152a 23 ± 3b 11 ± 1b
5 2.6 ± 0.5a 0.523 ± 0.089a 11 ± 1d 8 ± 1cd
6 2.4 ± 0.3ab 0.525 ± 0.361a 8 ± 1d 6 ± 2d
Means with different superscripts (a–d) are significantly different (p < 0:05).
*
Solvent: 50% ethanol.
462 K. Nazan Turhan, F. Sß ahbaz / Journal of Food Engineering 61 (2004) 459–466

4.0 Chinnan, 1995). Experimental results were within the


3.5 literature range. MC films are characteristically hydro-
3.0 2.64 g/100 mL solvent philic because of the functional hydroxyl groups they
X (g water/g ds)

1.32 g/100 mL solvent contain. Although MC is the least hydrophilic cellulose


2.5
0.66 g/100 mL solvent ether, MC films are still poor moisture barriers (Barrie,
2.0 1968; Biquet & Labuza, 1988; De Leiris, 1994; Kamper
1.5 & Fennema, 1984; Pascat, 1985; Schwartzberg, 1985).
1.0 For example, WVP of high and low density polyethylene
0.5
films is 0.0022 · 1010 and 0.0087 · 1010 g/m s Pa, re-
spectively (Guilbert & Biquet, 1996; Myers, Meyer,
0.0
0 20 40 60 80 100 Rogers, Stannet, & Szwarc, 1961). WVP of experimental
RH (%) MC films were 25–500 times greater than those of syn-
thetic films. However these films are better water vapor
Fig. 1. Adsorption isotherms of MC films containing different amounts
of PEG400 (T ¼ 25 C, solvent ¼ 50% ethanol). barriers than hydrophilic films based on starch, casein,
and wheat gluten (Allen, Nelson, Steinberg, & McGill,
1963; Aydt, Weller, & Testin, 1991; Gontard & Guilbert,
permeability might be expected to depend on the relative 1994; Greener & Fennema, 1989b; Kester & Fennema,
humidity (52–0%) to which the sample was exposed 1989; Schultz, Miers, Owens, & Maclay, 1949).
during testing. Ayrancı (1996) stated that the equili- The WVP of films with or without PEG400 and the
brium moisture content approached to zero as the RH effects of ethanol concentration in the film-forming so-
decreased below 35%, and at low water activities films lution were compared (Table 2). Column two shows that
did not adsorb water appreciably. Taking this point also WVP increased significantly as the ethanol concentra-
into account, the adsorption isotherms of various films tion increased. Ethanol is added to film-forming solu-
were determined at 25 C over the RH range of 52–98%. tions, because it allows a reduction in drying time due to
The equilibrium moisture content of the films was low at its low boiling point (78 C) and does not remain in the
RH ¼ 52%, and no significant difference was detected film after drying. Therefore it does not strongly modify
between them. Differences were notable as the PEG400 the structure of the polymer (Debeaufort & Voilley,
concentration increased (Fig. 1). In all films tested, 1997; Turhan et al., 2001). The ethanol concentration,
equilibrium moisture content increased almost linearly on the other hand, affects the solubility of MC, as evi-
up to an aw of 0.76–0.84, where a sharp increase was dent from the turbid appearance of films at high ethanol
noted. It was concluded that plasticization by water did concentrations indicating incomplete solubilization. The
not occur over the relative humidity range of experi- viscosity of these film-forming solutions was high, which
mental conditions. Therefore Eq. (1) can be used to made the removal of air bubbles difficult, and pinholes
calculate WVP at relative humidity difference of 52-0%, were formed. An increase in ethanol concentration in-
which is in linear portion of the sorption curves. creased WVP. Similar results were reported in a pre-
vious work (Perez-Gago et al., 1999).
3.2. Water vapor permeability However, no significant difference in WVP was found
between films prepared with 0–67% ethanol concentra-
The WVP of MC films was determined to be tions in the presence of PEG400 (Table 2, third column).
0.232 · 1010 –1.160 · 1010 g/m s Pa depending on the This result suggests that the plasticizing effect of
film composition. WVP of MC films was reported to be PEG400 overcame the difficulties arising from the de-
between 0.87 · 1010 and 1.47 · 1010 g/ m s Pa (Chinnan creasing solubility of MC as ethanol concentration in-
& Park, 1995; Donhowe & Fennema, 1993a, 1993b; creased. In fact, addition of PEG400 made the spreading
Kester & Fennema, 1989; Park et al., 1993; Park & easier, and much smoother films were obtained.

Table 2
The effects of EtOH and PEG400 on WVP
EtOH (%) Thickness (102 mm) WVP (g/s m Pa) · 1010
No PEG400 With PEG400 No PEG400 With PEG400
b b f
0 1.5 ± 0.3 1.6 ± 0.3 0.232 ± 0.012 0.697 ± 0.010bc
25 1.7 ± 0.2b 1.7 ± 0.1b 0.424 ± 0.048ef 0.745 ± 0.042b
50 1.7 ± 0.2b 1.8 ± 0.1b 0.514 ± 0.073cde 0.747 ± 0.075b
67 1.7 ± 0.3b 1.8 ± 0.2b 0.678 ± 0.052bd 0.829 ± 0.054b
75 2.3 ± 0.3a 2.4 ± 0.3a 1.086 ± 0.295a 1.160 ± 0.247a
Means with different superscripts (a–f) are significantly different (p < 0:05).
*
PEG400 ¼ 0.66 g/100 ml solvent.
K. Nazan Turhan, F. Sß ahbaz / Journal of Food Engineering 61 (2004) 459–466 463

Addition of plasticizers to the polymer matrix results compared as related to presence of ethanol concentra-
in an increase in WVP. But two different behaviors were tion and PEG400 (Table 4). The highest TS was ob-
observed in MC films. Incorporation of PEG400 to the served in the film prepared with water, and addition of
polymer matrix resulted in an increase in WVP at low ethanol and PEG400 decreased TS. Increasing PEG400
ethanol concentrations but had no effect at high con- concentration reduced TS, but no significant change was
centrations. This later result indicated that incomplete noted in the case of MW increase (Table 3).
solubilization of MC still appeared as the controlling The high TS values, observed in the films prepared
factor on the film structure; therefore, effect of PEG400 with water or water-ethanol, were attributed to the nu-
was not observed at high ethanol concentrations. merous hydrogen bonds between MC chains. These
The increase in WVP with increasing PEG400 con- bonds contribute to cohesiveness and low flexibility
centration is presented in Table 3. Addition of PEGs of unplasticized films (Turhan et al., 2001). When PEG
with various MWs resulted in increased WVP, although is incorporated in the MC network, a competition for
no difference was noted between their WVPs (Table 3). hydrogen bonding between MC–MC and MC–PEG
These were all expected results because PEG incorpo- occurs. As a result, direct interactions between MC
rated to the polymer matrix decreased the attractive chains are reduced partly due to hydrogen bond for-
forces between MC chains, increased free volume and mation with PEG or partly by the blocking effect of
segmental motions, hence water molecules diffused more high-molecular-weight PEGs. The concentration of
easily and higher WVP resulted. That the formation of PEG400 also significantly increased the hydrogen bond
hydrogen bonding between MC and PEG occurred, re- formation. This was strongly in accordance with the
ducing intermolecular attraction between MC–MC present observation that increasing PEG400 concentra-
chains, was also proven by the FTIR studies (Turhan tion decreased TS, due to increase of hydrogen bonding.
et al., 2001). Therefore PEGs reduce intermolecular attraction by
forming hydrogen bonds between MC chains or by
3.3. Tensile properties blocking the chains, allowing more flexibility and de-
creasing TS.
TS of MC films was determined to be 17–44 N/mm2 The incorporation of PEG to the polymer matrix
and %E between 14 and 97 depending on the film increased %E (Table 4). While the increase in MW of
composition. Mechanical properties for MC films were 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 (102 mm) WVP (g/m s Pa) · 1010 TS (N/mm2 ) E (%)
a d a
0 1.7 ± 0.2 0.514 ± 0.073 33 ± 3 14 ± 1a
0.33 1.7 ± 0.3a 0.620 ± 0.244bcd 30 ± 3a 20 ± 1b
0.66 1.8 ± 0.1a 0.747 ± 0.075ac 25 ± 2b 29 ± 2c
1.32 1.8 ± 0.3a 0.791 ± 0.089ab 19 ± 2c 74 ± 4d
2.64 1.9 ± 0.2a 0.875 ± 0.058a 17 ± 2c 97 ± 4e
PEG (MW)
400 1.8 ± 0.1a 0.747 ± 0.075a 25 ± 2a 29 ± 2a
1450 1.6 ± 0.1a 0.741 ± 0.048a 23 ± 2a 32 ± 2a
4000 1.6 ± 0.3a 0.732 ± 0.045a 27 ± 3a 21 ± 2b
8000 1.7 ± 0.1a 0.667 ± 0.042a 25 ± 2a 17 ± 1c
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 (102 mm) TS (N/mm2 ) E (%)
EtOH (0%) 1.5 ± 0.3a 44 ± 2a 14 ± 3a
EtOH (0%) + PEG400 1.6 ± 0.3a 22 ± 4c 38 ± 1b
EtOH (50%) 1.7 ± 0.1a 33 ± 3b 14 ± 1a
EtOH (50%) + PEG400 1.8 ± 0.2a 25 ± 2c 29 ± 1c
Means with different superscripts (a–c) are significantly different (p < 0:05).
*
0.66 g/100 ml solvent.
464 K. Nazan Turhan, F. Sß ahbaz / Journal of Food Engineering 61 (2004) 459–466

on %E appeared as the PEG concentration (Table 3). 100


Effects of PEG400 concentration on TS and %E were 90 %50 EtOH + PEG400
%0 EtOH + PEG400
different (Table 3). These differences correspond to the 80 %50 EtOH
glass transition of the polymer, which affects %E more 70 %0 EtOH
than TS (Debeaufort & Voilley, 1997). Depending on

SM (%)
60
the stress–strain curves, they classified MC-based films 50
into 4 groups. Using their work and the stress–strain 40
curves obtained in this research, the films containing no 30
PEG were classified as brittle and in the glassy state. 20
When PEG was incorporated, the resulting polymers 10
were classified as pseudoductile. Increases in %E mainly 0
occur when films become rubbery, i.e., when structure 0 20 40 60 80 100
changes from ductile to elastic (Debeaufort & Voilley, t (min)
1997). The %E increased significantly with the PEG400 Fig. 2. Effect of solution concentration and PEG400 (0.66 g/100 ml
content. At high PEG400 concentrations, the polymer solvent) and on solubility.
deforms homogeneously by viscous processes, given a
large extension to failure. This also was observed from
the shape of stress–strain curves. 100

Table 3 shows that MW of PEG did not affect WVP 90 PEG400


PEG1450
and TS of the films, but %E decreased slightly as the 80
PEG4000
MW of PEG increased. This can be attributed to the 70 PEG8000
heterogeneous film structure arising from the decrease of SM (%) 60
solubility and miscibility of high-molecular-weight 50
PEGs.
40
30
3.4. Film solubility
20

Solubility in water is an important property of edible 10

films. Potential applications may require water insolu- 0


0 20 40 60 80 100
bility to enhance product integrity and water resistance. t (min)
However, in some cases film water solubility before
Fig. 3. Effect of MW of PEG (0.66 g/100 ml solvent) on solubility.
consumption of the product might be benefical (Perez-
Gago et al., 1999).
The solubility of MC depends on its degree of sub- formation with PEG400. This result also was supported
stitution (DS), and MC used in this research (DS ¼ 1.9) by experiments during which the concentration of
was reported as water-soluble (Kirk & Othmer, 1963– PEG400 significantly increased the solution rate. This
1972). The dissolution of a hydrophilic polymer such as observation was in accordance with the report that in-
MC involves the penetration of water to the polymer termolecular hydrogen bonds between MC–MC chains
bulk and swelling. This is followed by disruption of were replaced by hydrogen bonds with PEG400 (Turhan
hydrogen and Van der Walls forces between polymer et al., 2001). As a result, the solvation of polar sites on
chains. Chemical degradation leading to the creation the MC chains and reduced intermolecular attraction
of oligomers and monomers occurs via hydrolysis or may be accountable for increased film water-solubility.
enzyme-catalysed hydrolysis (G€ opferich, 1996). Since Fig. 3 shows that %SM decreased as the MW of PEG
the hydrolysis of etheric bonds in MC was not possible increased. This may have resulted from the solubility
in basic solution such as the phosphate buffer (pH ¼ and hydrophilicity differences between PEG molecules,
7.4), MC was only hydrated and dissolved in this buffer. since both properties decrease with an increase in MW.
Films prepared only with water or water/ethanol In addition, higher numbers of edge groups in low MW
dissolved slowly, whereas plasticized film pieces dis- PEGs enable faster flow of water in the polymer matrix,
solved rapidly after coming into contact with water (Fig. resulting in higher dissolution rates.
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 4. Conclusion
hydrogen bonding also was observed in tensile proper-
ties. The increase in dissolution rate by the addition MC and ethanol concentrations in film-forming so-
of PEG400 was due to the disruption of native three- lutions strongly affected film structure, and unacceptable
dimensional structure of MC through hydrogen bond films were obtained at high concentrations. WVP and
K. Nazan Turhan, F. Sß ahbaz / Journal of Food Engineering 61 (2004) 459–466 465

%E increased and TS decreased with the addition of Greener, I. K., & Fennema, O. (1989a). Barrier properties and surface
various MW PEGs to the polymer matrix. Increasing characteristics of edible, bilayer films. Journal of Food Science,
54(6), 1393–1399.
PEG400 concentration increased WVP and %E and Greener, I. K., & Fennema, O. (1989b). Evaluation of edible, bilayer
decreased TS, but its effect was most pronounced on films for use as moisture barriers for food. Journal of Food Science,
%E. This was attributed to the glass transition of the 54(6), 1400–1406.
polymer to rubbery state. The films containing PEG had Greener, I., & Fennema, O. (1994). Edible films and coatings:
higher solubility, and solubility decreased as the MW of Characteristics, formation, definitions, and testing methods. In J.
K. Krocfta, E. A. Baldwin, & M. O. Nisperos-Carriedo (Eds.),
PEG increased. Structural differences between plasti- Edible coatings and films to improve food quality (pp. 1–24). USA:
cized and unplasticized films were explained in terms of Technomic.
hydrogen bonding between PEG and MC chains or a Guilbert, S., & Biquet, B. (1996). Edible films and coatings. In G.
blocking effect in the case of high-MW PEGs. Bureau, & J. L. Multon (Eds.), Food Packaging Technology (vol. 1,
p. 528). New York: VCH Publishers.
Kamper, S. L., & Fennema, O. (1984). Water vapor permeability of
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