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Germadios,
H. Gooding b
ABSTRACT
Water vapor transmission WVT of films is commonly measured using
modifications of the ASTM E 96 Standard Method (cup method). A
stagnant air layer exists between the underside of the filmmounted on the
cup and the sueace of the desiccant, saturated salt solution or distilled
water contained in the cup. The method considers the air gap resistance to
be negligible to water vapor transport. When high water vapor-transmitting hydrophilic edible films are measured with the cup method, the
resistance of the stagnant air layer can be significant and, if neglected, can
lead to underestimation of water vapor transmission rates. Equations
were presented in this study to correct WVTdata for the air gap resistance.
For both a methylcellulose and a corn zein film, water vapor permeabilities measured with air gaps of 1.0 and I.5 cm were statistically significantly
(a = O-05) different. Values corrected to account for air gap resistance were
not statistically significantly (a = 005) different. Literature data on water
vapor permeability of other hydrophilic edible films were corrected to
account for the air layer resistance. Underestimation of actual values
ranged between 5 and 46X.
NOTATION
A
396
4,
hi
L
NJ
P
Pr
Pwo
PWI
Pw2
PW3
w,
T
WVTR,
WVTR,
APa
AP,
Air gap between film and desiccant suspended over film (cm)
Air gap between film and surface of distilled water, saturated
salt solution or desiccant in the cup (cm)
Fihn thickness (m)
Measured value of water vapor transmission (WVT ) rate (g
mol/cm2 s)
Vapor pressure of water at the temperature of the test (Pa)
Total atmospheric pressure (Pa)
Partial pressure of water vapor in air at the surface of distilled
water, saturated salt solution or desiccant in the cup (Pa)
Partial pressure of water vapor at underside of fihn (Pa)
Partial pressure of water vapor at the fihn surface outside the
cup (Pa)
Partial pressure of water vapor at the underside of desiccant
suspended over film and cup (Pa)
Corrected water vapor permeability (g/m s Pa)
Measured water vapor permeability (g/m s Pa)
Universal gas constant (8 306 600 Pa cm3/g mole K)
Relative humidity over distilled water, saturated salt solution
or desiccant inside the cup (Oh)
Relative humidity outside the cup (Oh)
Absolute temperature during testing (K)
Corrected value of WVT rate (g/m2 day)
Measured value of WVT rate (g/m2 day)
Apparent water vapor partial pressure difference across the
film (Pa)
Real water vapor partial pressure difference across the film
(Pa)
INTRODUCTION
Edible films and coatings from proteins, polysaccharides and lipids have
received increased interest in recent years as potential food protective
materials. Research findings on production, properties and potential
applications of edible films have been recently reviewed (Guilbert, 1986,
1988; Kester & Fermema, 1986; Krochta, 1992). Protein-based films
from wheat, corn and soy proteins have been discussed by Gennadios
and Weller (1990, 1991). WVT of these films is an important property,
indicating their ability to control water vapor transport between a food
system and its surroundings.
397
398
399
vapor permeability
literature.
values of hydrophilic
MATERIALS
in the
AND METHODS
(1)
(2)
cup-
/////////.
/////////.
////f////.
exp(NwhilcD
+ -
water,
saturated salt solution
or desiccant
/////////.
/////////.
Fig. 1.
measurement
cup indicating
400
where
N,=(6.43
Molar concentration
x lo-)WVTR,
(4)
(5)
The diffusion coefficient (II) at 1.013 X lo5 Pa ( 1 atm) can be estimated by the following empirical equation (Bretsznajder, 197 1):
D= (O-26)( T/298)8
The corrected value of water vapor transmission
WVTR, = WVTR,KP,,
2nd Case: RH, < RH,, h, = 0
(6)
rate is given by
P~Z)/(P,, - P~Z11
(7)
1nthiscasep,,<p,,<p,,,p,,=pRH,/100,andp,,=pRH2/100.
APa = Pw2 - Pwo
(8)
(9)
Pwl=P~-(P~-PwO)exP
WV%
~%KP,~
(-NwhilcD)
- ~woY(~w2
(10)
- pwl )I
01)
(12)
(13)
Both pw, and pw2 are unknowns. Equation (3) can be used to calculate
pw2 we have
pw , . For
pw3=pT-(pT-~w2)
exp (Kh0lcD)
(14)
Pw2=PT-(PT-Pw3)exp(-N,h0/cD)
- pw3
)/(P,, - pw2 )I
(16)
can be calculated by
x 105)WVTR,L/Ap,
(17)
The coefficient
conversions.
401
P, = (1.157 x lO+)WVTR,L/Ap,
(18)
P, = (1.157 x 10-5)WVTR,L/Ap,
(19)
equations
satisfies
unit
402
(B.C. Ames, Waltham, MA, USA) to the nearest 254 pm. Five
measurements were taken on each specimen, one at the center and four
around the perimeter, and their mean was used as the specimen thickness.
Measurement of WVT rate
Cups used to determine WVTR,,, were manufactured at the Department
of Agricultural and Biological Engineering at Clemson University by
modifying an original design provided by Dr J. M. Krochta (Department
of Food Science and Technology, University of California, Davis, CA,
USA). Each consisted of a cylindrical bottom made of poly(methy1
methacrylate) (Piedmont Plastics, Greenville, SC, USA), a lid of the
same material, and a rubber O-ring (Fig. 2). The bottom had a diameter
of 8.7 cm. A well 4.6 cm in diameter and 2.1 cm in depth was milled into
the bottom. An O-ring (internal diameter 5.6 cm) was placed into a
groove milled around the well. Four screws, symmetrically placed
around the cup perimeter, were tightened to hold film specimens
securely between the lid and the bottom part. Good sealing of film specimens between lid and bottom was provided by the O-ring.
Machine Screws
Fig. 2.
403
= Slope/A
(20)
Equations (3) and (7) were used to calculate pwl and WVTR,, respectively. Values of P,,, and P, were also calculated from eqns ( 17) and ( 18),
respectively.
404
TABLE 1
Measured Water Vapor Permeability Values of Methyl Cellulose and Corn Zein Edible
Films and Corrected Values to Account for Stagnant Air Layer Resistance~b~c
Airgap
(cm)
P, x IO
P, x 1o0
Errold
(g/m s Pa)
(g/m s Pa)
(%)
1.0
15
26 f 0.3
2.1 f 0.1
1.0
l-5
4.0 + 0.2
3.4 _+0.2
Methyl cellulose
6.2 f 05
6.1 + 0.4
Corn zein
5.1+ 0.3
49k@4
58
66
22
31
Measured and corrected permeability values are the mean of eight samples plus/minus
one standard deviation.
hTesting conditions were 25C and 50% (lOO%-50%) relative humidity gradient across
the films.
cMean thickness of the methyl cellulose and the corn zein films were 23 f. 1 pm and
89 f 10 pm, respectively.
Error was calculated as [(PC- P,,,)/P,]lOO.
405
lene glycol and beeswax (Kamper & Fermema, 1984) was within 0.02%
of the reported WVTR, value. For a 14.7 pm thick hydroxypropyl
methycellulose film containing 42% stearic acid (Hagenmaier & Shaw,
1990) the calculated corrected value was within 0.2% of the measured
value.
The effect on WVT of a stagnant air layer in the cup was noticed by
Schultz et al. (1949) in their water vapor transmission rate study of
pectinate films. The transmission rate of a calcium sodium pectinate film
was reduced by 5% when the dead air space was increased by 50%.
From this observation these researchers concluded that the error introduced by the whole dead air space did not exceed 11%. Their conclusion
assumed a linear relationship between air gap depth and error introduced from it, which is erroneous as illustrated by the equations presented here. Some permeability values from Schultz et al. (1949) were
corrected to account for air space, and an error of 30 to 41% was estimated (Table 2).
In a few recently conducted studies, Permatran-W measuring systems
(Macon, Minneapolis, MN) were used to determine water vapor permeability of edible films (Greener & Fennema, 1989a, b; Kester &
Fennema, 1989b; Germadios et al., 1990, 1993). These systems operate
according to the ASTM Standard Method F 1249-89 (ASTM, 1989).
Film specimens are mounted between the upper and lower halves of
temperature-controlled
diffusion cells. A couple of absorbent pads
moistened with distilled water or saturated salt solution to achieve a
desired RH, are placed in the lower half of the cells. Water vapor transmitted through the films is carried to an infrared detector by dry nitrogen
(RH, = 0%) flowing over the upper side of films. As with the cup
method, an air gap of O-2 to 0.3 cm exists between the saturated pads
and the underside of the film. When edible barriers that are high water
vapor transmitters are tested, the effect of this gap could be important.
The underestimation
error would be greater than 5% when WVTR,
values approach or exceed 1000 g/m* day. Gennadios et al. ( 1990,199 1)
used a Permatran-W600
instrument to measure WVT rates of wheat
gluten-based films at 23C and RH, = 11%. Due to the small relative
humidity gradient applied across the films, errors induced by neglecting
air gap resistance were smaller than 2%.
CONCLUSIONS
Water vapor permeability values of highly permeable, hydrophilic edible
films, as determined with the cup method, are underestimated when air
gap resistance in the cup is neglected. Furthermore, since the magnitude
( 1990)
(1990)
(1990)
(1990)
125
140
89
38
28
8
19
Thickness
(pm)
TABLE 2
Edible Films as Reported
Resistance
Wheat gluten/glycerin
Corn zein/glycerin
(Hydroxypropyl)methylcellulose
(Hydroxypropyl)methylcellulose
(Hydroxypropyl)methylcellulose
(Hydroxypropyl)methylcellulose
+ 2% steak acid
(Hydroxypropyl)methylcellulose
+ 42% stearic acid
(Hydroxypropyl)methylcellulose
/Polyethylene glycol
/Hydrogenated cottonseed and
soybean oils
Film
Values of Hydrophilic
Reference
1.8
O-08
12.5
4.1
1.3
0.7
O-5
0.7
P,, x IO
Mm s Pa)
l-9
O-09
23.1
5.3
1.7
0.9
0.8
@9
11
46
23
24
22
38
22
50/100% RH
50/100% RH
O/85% RH
O/85% RH
O/85% FW
O/85% RH
25C 85/O% RH
27C, O/85% RH
26C,
26c,
27C.
27C,
27C,
27C,
Conditio&
Error L1
(W
and Corrected
P, x 100
(glm s Pa)
in the Literature
ef al. ( 1958)
et al. (1958)
et al. ( 1949)
et al. (1949)
et al. ( 1949)
et al. ( 1949)
Methylcellulose
Wheat gluten/glycerin
Methylcellulose/polyethylene
glycol
(Hydroxypropyl)methylcellulose
/Polyethylene glycol
Amylose
Amylose
Sodium hydrogen pectinate
Calcium sodium pectinate
Calcium sodium pectinate
Calcium sodium
Pectinate/glycerin
3.3
2.2
6-l
6.1
7.7
8.7
1.1
50
29
29
27
35
35
46
0.145
6.2
0.9
5
400
55
3.6
3.8
10.0
8.8
13.1
12.9
1.3
0.152
7.0
1.1
8
42
39
31
41
33
15
5
11
18
25C, 100/l% RH
25C 8 l/29% RH
25C 81/31%RH
25C 81/31%RH
3.5C, 78/40% RH
25C 81/31%RH
21C 85/O% RH
37.8C, 91/O%RH
21C 85/O% RH
21C 85/O% RH
Rankin
Rankin
Schultz
Schultz
Schultz
Schultz
3
B
g
Q
*
&
g
408
of the air gap varies between different research studies, accounting for
stagnant air layer resistance is an essential requirement prior to comparing water vapor permeabilities of hydrophilic edible Nms and coatings
developed and tested at different laboratories.
ACKNOWLEDGEMENTS
This research was supported by a South Carolina Agricultural Experiment Station Enhancement in Packaging Research Competitive Grant.
Technical Contribution No. 3301 of the South Carolina Agricultural
Experiment Station, Clemson University, Clemson, SC, USA.
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1.
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199.
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409
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